Method for preparing silane derivatives from furan derivatives in presence of borane catalyst

ABSTRACT

The present invention relates to a method for preparing various silane derivatives by subjecting various furan derivatives to hydrosilylation in the presence of a borane catalyst. The method for preparing silane derivatives according to the present invention is a very efficient method for converting, into high value-added silane derivatives, various furan derivatives derived from biomass.

TECHNICAL FIELD

The present invention relates to a method of preparing a silanederivative from various furan derivatives in the presence of a boranecatalyst, and more particularly, to a method of preparing a silanederivative that is available as a raw material, an intermediate, and thelike in various fields using a borane catalyst from various furanderivatives from biomass.

BACKGROUND ART

Currently, crude oil is the most important raw material to produce finechemical substances, polymer materials, or medicines. However, there isa need to develop alternatives for replacing crude oil along withreduction in oil reserves as well as an environmental problem due tocollection, transportation, and refinement of crude oil.

Biomass has emerged as one of these alternatives. Biomass may be animportant source for producing hydrocarbon and chemical substances witha high added value.

Accordingly, recently, research has been conducted in various ways intoa reaction for entire or partial reduction of cellulose to preparebioethanol, hydrocarbon, or synthesized intermediate.

Various furan derivatives including furfural, hydroxymethyl furfural(HMF) and derivatives from biomass thereof are capable of being used asa raw material and intermediates of various chemical substances and,thus, may be an important raw material.

Although a furan derivative is capable of being inexpensively and easilyobtained from carbohydrate, numerous researches into a reaction of afuran derivative using a metallic catalyst have been reported, but thereis still a need for research into a reaction of a furan derivative thatis capable of being commercially mass-produced due to a high yield underan eco-friendly or mild condition without using transition metal.

For example, Green Chem. 16, 516-47 (2014) discloses a method ofpreparing a biomass-derived material including furan or the like as afunctional group in the form of a liquid fuel, or the like via variousreactions.

DISCLOSURE Technical Problem

An object of the present invention is to provide a method of preparing asilane derivative via hydrosilylation of various furan derivatives inthe presence of a borane catalyst.

Another object of the present invention is to provide various silanederivatives prepared via hydrosilylation of various furan derivatives inthe presence of a borane catalyst.

Technical Solution

The present invention may provide a method of preparing a silanederivative from various furan derivatives in the presence of a boranecatalyst, and more particularly, a method of preparing various silanederivatives with high stereoselectivity and a high yield under a mildcondition through hydrosilylation of a furan derivative in the presenceof a borane catalyst, and silane derivative prepared using the method.

The method of preparing the silane derivative according to the presentinvention may be very effective to obtain a silane derivative with ahigh yield by performing hydrosilylation of a furan derivative and asilane compound under a mild condition in the presence of a boranecatalyst.

The method of preparing the silane derivative according to the presentinvention may be advantageous to have a high yield because a byproductis almost barely present and to be commercially mass-produced with veryhigh stereoselectivity and a very high conversion yield.

The present invention provides a method of preparing ananti-(2-alkyl)cyclopropyl silane derivative with an organic silyl groupintroduced to a specific location, which is available as an importantintermediate and synthon to synthesize various medicines andagricultural chemical material, and more particularly, a method ofpreparing an anti-(2-alkyl)cyclopropyl silane derivative with a highyield via high stereoselectivity under a mild condition throughring-opening, hydrosilylation, and cyclization of various furancompounds from biomass using silane compound in the presence of a boranecatalyst, and an anti-(2-alkyl)cyclopropyl silane derivative preparedusing the method.

The method of preparing an anti-(2-alkyl)cyclopropyl silane derivativeaccording to the present invention may be very effective to obtain ananti-(2-alkyl)cyclopropyl silane derivative with a high yield via highstereoselectivity through ring-opening, hydrosilylation, and cyclizationof various furan compounds and silane compounds in one pot under a mildcondition in the presence of a borane catalyst.

In addition, the method of preparing an anti-(2-alkyl)cyclopropyl silanederivative according to the present invention may be advantageous to becommercially mass-produced due to a high yield, very highstereoselectivity, and a very high conversion yield.

In more detail, the present invention may relate to two aspects of (I) amethod of preparing a silane derivative obtained via ring-opening of afuran compound via a reaction between a silane compound and furancompound from biomass and (II) a method of preparing a cyclopropylsilane derivative via a reaction between a silane compound and a furancompound from biomass.

Hereinafter, the method of preparing a ring-opened silane derivativeobtained via a reaction between a furan compound and a silane compound,of the above two aspects according to the present invention, will bedescribed in detail and includes five aspects in detail.

As the aspect (I-1) above, a method of preparing a silane derivativerepresented by Chemical Formula 1 may include preparing Chemical Formula1 via a reaction between Chemical Formula 2 and a silane compound ofChemical Formula 3 in the presence of a borane catalyst.

In Chemical Formulae 1 to 3,

R₁ is C₁-C₁₀ alkyl or C₆-C₂₀ aryl with a radical number depending on n;

R₁₁ to R₁₃ are each independently C₁-C₁₀ alkyl or C₆-C₁₂ aryl;

n is an integer of 1 to 3 and, when n is equal to or greater than 2, R₁is C₆-C₁₂ aryl; and

alkyl and aryl of R₁ are further substituted with any one selected fromhalogen, C₁-C₁₀ alkyl, halo C₁-C₁₀ alkyl, thio C₁-C₁₀ alkyl, C₁-C₁₀alkoxy, C₆-C₁₂ aryl, C₆-C₁₂ aryloxy, and —OSi(R₂₁)(R₂₂)(R₂₃) and R₂₁ toR₂₃ are each independently C₁-C₁₀ alkyl or C₆-C₁₂ aryl.

The method of preparing the silane derivative according to the presentinvention may be very effective to obtain a silane derivativerepresented by Chemical Formula 1, in more detail, a siloxyalkenylsilanederivative with a high yield under a mild condition via a reactionbetween a furan derivative represented by Chemical Formula 2 and asilane compound represented by Chemical Formula 3 in the presence of aborane catalyst.

In the method of preparing the silane derivative according to thepresent invention, an α-siloxy-Z-alkenylsilane derivative may beprepared with a high yield via high stereoselectivity because abyproduct is almost barely present.

According to the present invention, in the case in which R₁ is C₆-C₂₀aryl with a radical number depending on n, when n is 2, R₁ may bearylene (e.g., penylene) with two radicals and, when n is 3, R₁ may be,for example,

Chemical Formula 1 according to an embodiment of the present inventionmay be represented by Chemical Formula 1-1 and Chemical Formula 2 may berepresented by Chemical Formula 2-1.

In Chemical Formulae 1-1 and 2-1,

R₂ may be C₁-C₁₀ alkyl or C₆-C₁₈ aryl;

R₁₁ to R₁₃ may be each independently C₁-C₁₀ alkyl or C₆-C₁₂ aryl;

alkyl and aryl of R₂ may be further substituted with any one selectedfrom halogen, C₁-C₁₀ alkyl, halo C₁-C₁₀ alkyl, thio C₁-C₁₀ alkyl, C₁-C₁₀alkoxy, C₆-C₁₂ aryl, C₆-C₁₂ aryloxy, and —OSi(R₂₁)(R₂₂)(R₂₃), and R₂₁ toR₂₃ may each independently be C₁-C₁₀ alkyl or C₆-C₁₂ aryl.

In Chemical Formulae 1-1 and 2-1, R₂ may be C₁-C₇ alkyl or C₆-C₁₅ aryl,alkyl and aryl of R₁ may be further substituted by any one selected fromhalogen, C₁-C₁₀ alkyl, halo C₁-C₁₀ alkyl, thio C₁-C₁₀ alkyl, C₁-C₁₀alkoxy, C₆-C₁₂ aryl, C₆-C₁₂ aryloxy, and —OSi(R₂₁)(R₂₂)(R₂₃), and R₂₁ toR₂₃ may each independently be C₁-C₁₀ alkyl or C₆-C₁₂ aryl.

Chemical Formula 1 may be represented by Chemical Formula 1-2 andChemical Formula 2 may be represented by Chemical Formula 2-2.

In Chemical Formulae 1-2 and 2-2,

R₁₁ to R₁₃ may each independently be C₁-C₁₀ alkyl or C₆-C₁₂ aryl;

n may be an integer of 1 to 3;

R₁₄ may be halogen, C₁-C₁₀ alkyl, halo C₁-C₁₀ alkyl, thio C₁-C₁₀ alkyl,C₁-C₁₀ alkoxy, C₆-C₁₂ aryl, C₆-C₁₂ aryloxy, or —OSi(R₂₁)(R₂₂)(R₂₃);

R₂₁ to R₂₃ may each independently be C₁-C₁₀ alkyl or C₆-C₁₂ aryl; and

s may be an integer of 0 or 1 to 4 and n+ s≤6.

In Chemical Formulae 1-2 and 2-2, n may be an integer of 2 to 3;

R₁₄ may be halogen, C₁-C₁₀ alkyl, halo C₁-C₁₀ alkyl, thio C₁-C₁₀ alkyl,C₁-C₁₀ alkoxy, C₆-C₁₂ aryl, or C₆-C₁₂ aryloxy.

The present invention may provide a silane derivative of ChemicalFormula 1 prepared via hydrosilylation of furan derivative in thepresence of a borane catalyst.

In detail, a silane derivative of Chemical Formula 1 may be selectedfrom the following compounds but is not limited thereto.

Second, (I-2) a method of preparing a silane derivative represented byChemical Formula 4 according to the present invention may includepreparing Chemical Formula 4 via a reaction between Chemical Formula 5and Chemical Formula 3 in the presence of a borane catalyst.

In Chemical Formulae 3 to 5,

R₃ may be hydrogen, C₁-C₁₀ alkyl, or C₆-C₁₂ aryl;

R₁₁ to R₁₃ may each independently be C₁-C₁₀ alkyl or C₆-C₁₂ aryl;

alkyl and aryl of R₃ may be further substituted with any one selectedfrom halogen, C₁-C₁₀ alkyl, halo C₁-C₁₀ alkyl, thio C₁-C₁₀ alkyl, C₁-C₁₀alkoxy, C₆-C₁₂ aryl, C₆-C₁₂ aryloxy, and —OSi(R₂₁)(R₂₂)(R₂₃) and R₂₁ toR₂₃ may each independently be C₁-C₁₀ alkyl or C₆-C₁₂ aryl.

In Chemical Formulae 4 to 5, R₃ may be hydrogen or C₆-C₁₂ aryl.

The present invention may provide a silane derivative represented byChemical Formula 4.

Third, (I-3) a method of preparing a silane derivative represented byChemical Formula 6 according to the present invention may includepreparing Chemical Formula 6 via a reaction between Chemical Formula 7and Chemical Formula 3 in the presence of a borane catalyst.

In Chemical Formulae 3, 6, and 7,

R₄ and R₅ may each independently be C₁-C₁₀ alkyl or C₆-C₁₂ aryl;

R₁₁ to R₁₃ may each independently be C₁-C₁₀ alkyl or C₆-C₁₂ aryl; and

alkyl and aryl of R₄ and R₅ may be further substituted with any oneselected from halogen, C₁-C₁₀ alkyl, halo C₁-C₁₀ alkyl, thio C₁-C₁₀alkyl, C₁-C₁₀ alkoxy, C₆-C₁₂ aryl, C₆-C₁₂ aryloxy, and—OSi(R₂₁)(R₂₂)(R₂₃), and R₂₁ to R₂₃ may each independently be C₁-C₁₀alkyl or C₆-C₁₂ aryl.

In Chemical Formulae 6 and 7, R₄ and R₅ may each independently be C₁-C₁₀alkyl, and alkyl of R₄ and R₅ may be further substituted with halogen,C₁-C₁₀ alkyl, or halo C₁-C₁₀ alkyl.

The present invention may provide a silane derivative represented byChemical Formula 6.

Fourth, (I-4) a method of preparing a silane derivative represented byChemical Formula 8 according to the present invention may includepreparing Chemical Formula 8 via a reaction between Chemical Formula 9and Chemical Formula 3-1 in the presence of a borane catalyst.

In Chemical Formulae 3-1 and 8 to 9,

R₆ and R₇ may each independently C₁-C₁₀ alkyl or C₆-C₁₂ aryl;

R₁₁ and R₁₂ may each be C₆-C₁₂ aryl in the same way; and

alkyl and aryl of R₆ and R₇ may be further substituted with any oneselected from halogen, C₁-C₁₀ alkyl, halo C₁-C₁₀ alkyl, thio C₁-C₁₀alkyl, C₁-C₁₀ alkoxy, C₆-C₁₂ aryl, C₆-C₁₂ aryloxy, and—OSi(R₂₁)(R₂₂)(R₂₃) and R₂₁ to R₂₃ may each independently C₁-C₁₀ alkylor C₆-C₁₂ aryl.

In Chemical Formulae 8 and 9, R₆ and R₇ may each independently C₁-C₁₀alkyl, and alkyl of R₆ and R₇ may be further substituted with any oneselected from halogen, C₁-C₁₀ alkyl, halo C₁-C₁₀ alkyl, and C₁-C₁₀alkoxy.

The present invention may provide a silane derivative of ChemicalFormula 8.

Fifth, (I-5) a method of preparing a silane derivative represented byChemical Formula 10 may include preparing Chemical Formula 10 via areaction between Chemical Formula 11 and Chemical Formula 3 in thepresence of a borane catalyst.

In Chemical Formulae 3, 10, and 11,

R₈ may be hydrogen, C₁-C₁₀ alkyl, or C₆-C₁₂ aryl;

R₁₁ to R₁₃ may each independently C₁-C₁₀ alkyl or C₆-C₁₂ aryl; and

alkyl and aryl of R₈ may be further substituted with any one selectedfrom halogen, C₁-C₁₀ alkyl, halo C₁-C₁₀ alkyl, thio C₁-C₁₀ alkyl, C₁-C₁₀alkoxy, C₆-C₁₂ aryl, C₆-C₁₂ aryloxy, and —OSi(R₂₁)(R₂₂)(R₂₃), and R₂₁ toR₂₃ may each independently C₁-C₁₀ alkyl or C₆-C₁₂ aryl.

In detail, the silane derivative represented by Chemical Formula 10according to the present invention may be prepared by preparing ChemicalFormula 12 from Chemical Formula 11 and, then, preparing ChemicalFormula 10 from Chemical Formula 12 under base.

In Chemical Formula 12,

R₈ may be hydrogen, C₁-C₁₀ alkyl, or C₆-C₁₂ aryl;

R₁₁ to R₁₃ may each independently C₁-C₁₀ alkyl or C₆-C₁₂ aryl; and

alkyl and aryl of R₈ may be further substituted with any one selectedfrom halogen, C₁-C₁₀ alkyl, halo C₁-C₁₀ alkyl, thio C₁-C₁₀ alkyl, C₁-C₁₀alkoxy, C₆-C₁₂ aryl, C₆-C₁₂ aryloxy, and —OSi(R₂₁)(R₂₂)(R₂₃), and R₂₁ toR₂₃ may each independently C₁-C₁₀ alkyl or C₆-C₁₂ aryl.

The base according to an embodiment of the present invention may be anybase that is recognizable by one of ordinary skill in the art but, forexample, may be one or two or more selected from K₂CO₃, andtetra(n-butyl)ammoniumfluoride (TBAF) and may be used in 1.5 to 2.5moles based on 1 mol of the furan derivative.

The present invention may provide a silane derivative represented byChemical Formula 10.

In detail, the silane derivative represented by Chemical Formula 10 maybe selected from the following compounds but is not limited thereto.

In the specification, the “alkyl”, “alkoxy” and other substitutioncompounds including a part “alkyl” may include any linear or branchedchain and may have C₁-C₁₀ atoms, in detail, C₁-C₇ atoms, in more detail,C₁-C₅ atoms. An example thereof may include methyl, ethyl, propyl,isopropyl, butyl, isobutyl, t-butyl, pentyl, hexyl, octyl, and nonyl butis not limited thereto.

The “haloalkyl” stated in the specification may refer to substitution ofone or more hydrogen coupled to a carbon atom of an alkyl group withhalogen and, for example, may be trifluoromethyl.

The “aryl” stated in the specification may be an organic radical derivedfrom aromatic hydrocarbon by removing one hydrogen, and each ring mayappropriately include a single or fused ring system including 4 to 7ring atoms, in detail, 5 or 6 ring atoms, and may also include aplurality of aryls connected via single bond. An example thereof mayinclude phenyl, naphthyl, biphenyl, anthryl, indenyl, and fluorenyl butis not limited thereto.

The term “aryloxy” stated in the specification may refer to -O-arylradical and, here, the ‘aryl’ is defined as described above. An exampleof the aryloxy radical may include phenoxy and naphthoxy but is notlimited thereto.

The term “alkylthio” stated in the specification may refer to -S-alkylradical and, here, the ‘alkyl’ is defined as described above. An exampleof the alkylthio radical may include methylthio and ethylthio but is notlimited thereto.

The term “arylene” stated in the specification may be an organic radicalderived from aromatic hydrocarbon by removing two hydrogen and mayinclude phenylene, biphenylene, fluorenylene, naphthylene,anthracenylene, or the like but is not limited thereto.

The furan derivative stated in the specification may be a compoundderived from crude oil, biomass, and so on and may be synthesized andused using a general synthesis method.

The borane catalyst according to an embodiment of the present inventionmay be one or two or more selected from B(C₆F₅)₃, (C₆F₅CH₂CH₂)B(C₆F₅)₂,(CF₃(CF₂)₃(CH₂)₂B(C₆F₅)₂, HB(C₆F₅)₂, B(C₆H₅)₃, and ClB(C₆F₅)₂, may beeasily handled due to stability in the air, and may be one or two ormore selected from B(C₆F₅)₃, HB(C₆F₅)₂, and (C₆F₅CH₂CH₂)B(C₆F₅)₂ interms of reaction efficiency.

In the method of preparing the silane derivative according to anembodiment of the present invention, the borane catalyst may be used in0.015 to 0.025 mol (1.5 to 2.5 mol %) based on 1 mol of a furanderivative, i.e., compound represented by Chemical Formula 2, ChemicalFormula 5, Chemical Formula 7, Chemical Formula 9, or Chemical Formula11 and, in detail, the borane catalyst may be used in 0.015 to 0.025mol, in detail, 0.019 to 0.021 mmol (1.9 to 2.1 mol %) based on 1 mol ofa furan derivative as a start material with respect to one furanfunctional group (e.g.,

of the start material.

In the method of preparing the silane derivative according to anembodiment of the present invention, R₁₁ to R₁₃ in Chemical Formula 3that is a silane compound may each independently C₁-C₁₀ alkyl or C₆-C₁₂aryl but one or more of R₁₁ to R₁₃ may be alkyl. That is, R₁₁ to R₁₂ mayeach independently alkyl, R₁₃ may be aryl or R₁₁ may be alkyl, R₁₂ andR₁₃ may be aryl, R₁₁ to R₁₂ may each independently alkyl, and R₁₃ may bearyl in terms or reaction efficiency. An example of Chemical Formula 3may be Si(Ph)(Me)₂(H).

With regard to Chemical Formula 3 in the method of preparing the silanederivative according to the present invention, the silane derivative maybe used with 2.0 to 2.5 moles, in detail, 2.0 to 2.2 moles based on 1mol of a furan derivative, i.e., a compound represented by ChemicalFormula 2, Formula 5, Chemical Formula 7, or Chemical Formula 11, indetail, based on 1 mol of a furan derivative with respect to one furanfunctional group of a furan derivative, i.e., a compound represented byChemical Formula 2, Chemical Formula 5, Chemical Formula 7, or ChemicalFormula 11.

For example,

that is the furan derivative according to the present invention hasthree furan functional groups and, thus, a borane catalyst may be usedin 6 mol % based on 1 mol of

and the silane derivative may be used in 6 moles.

In Chemical Formula 3-1 in the method of preparing the silane derivativeaccording to an embodiment of the present invention, unlike in ChemicalFormula 3, R₁₁ and R₁₂ may each independently C₁-C₁₀ alkyl or C₆-C₁₂aryl and, in detail, R₁₁ and R₁₂ may each independently aryl.

For example, Chemical Formula 3-1 may be Si(Ph)₂(H)₂ and the furanderivative, i.e., a compound of Chemical Formula 3-1 may be used in 2.0to 2.5 moles, in detail, 2.0 to 2.2 moles based on 1 mol of a furanderivative, i.e., a compound of Chemical Formula 9.

According to an embodiment of the method of preparing a silanederivative of the aspect I of the present invention, in the boranecatalyst and the silane compound represented by Chemical Formula 3, theborane catalyst may be B(C₆F₅)₃ and Chemical Formula 3 may be PhMe₂SiHas a combination in terms of reaction efficiency and, as an idealcombination of the borane catalyst and Chemical Formula 3-1, the boranecatalyst may be B(C₆F₅)₃ and Chemical Formula 3 may be Ph₂SiH₂.

In the aspect I of the present invention, a reaction solvent in themethod of preparing the silane derivative may be any solvent that isgenerally used in a general organic reaction and, for example, may bedichloromethane, chloroform, toluene, and chlorobenzene but, may be adichloromethane in the combination of B(C₆F₅)₃ and PhMe₂SiH or B(C₆F₅)₃and Ph₂SiH₂.

In the aspect I of the present invention, reaction temperature andreaction time during preparation of a silane derivative are not limitedbut, a reaction may be performed at a reaction temperature, e.g., roomtemperature, at 15 to 35° C. for 1 hour to 12 hours, and at 18 to 30° C.for 1 hour to 5 hours in terms of reaction efficiency.

The second aspect (II) may provide a method of preparing a cyclopropylsilane derivative via a reaction between a silane compound and a furancompound from biomass.

As the second aspect, the method of preparing ananti-(2-alkyl)cyclopropyl silane derivative in presence of a boranecatalyst may include four methods and will be described in detail.

First, as the first aspect (II-1), the present invention may include amethod of preparing an anti-(2-alkyl) cyclopropyl silane derivative ofChemical Formula 21-1 via a reaction between a furan compoundrepresented by Chemical Formula 22-1 and a silane compound representedby Chemical Formula 23 in the presence of a borane catalyst.

In Chemical Formulae 21-1, 22-1, and 23,

R may be C₁-C₂₀ alkyl, C₆-C₂₀ aryl, or C₆-C₂₀ aryl C₁-C₂₀ alkyl, andalkyl, aryl, or arylalkyl of R may be further substituted with one ormore selected from the group consisting of halogen, C₁-C₂₀ alkyl, haloC₁-C₂₀ alkyl, C₁-C₂₀ alkoxy, C₆-C₂₀ aryl, C₆-C₂₀ aryloxy, and C₁-C₂₀alkylthio;

R^(a) to R^(c) may each independently hydrogen, C₁-C₂₀ alkyl, or C₆-C₂₀aryl;

R^(d) may be hydrogen or heavy hydrogen; and

R^(a) to R^(c) may not be simultaneously hydrogen.

The present invention may provide a method of preparing ananti-(2-alkyl) cyclopropyl silane derivative of Chemical Formula 21-1via a reaction between an α-silyloxy-(Z)-alkenyl silane derivative ofChemical Formula 24 and a silane compound represented by ChemicalFormula 23 in the presence of a borane catalyst.

In Chemical Formulae 21-1, 23, and 24,

R may be alkyl, C₁-C₂₀ alkyl, C₆-C₂₀ aryl, or C₆-C₂₀ aryl C₁-C₂₀ alkyl,and alkyl, aryl, or arylalkyl of R may be further substituted with oneor more selected from the group consisting of halogen, C₁-C₂₀ alkyl,halo C₁-C₂₀ alkyl, C₁-C₂₀ alkoxy, C₆-C₂₀ aryl, C₆-C₂₀ aryloxy, andC₁-C₂₀ alkylthio;

R₁₁ to R₁₃ may each independently C₁-C₂₀ alkyl or C₆-C₂₀ aryl;

R^(a) to R^(c) may each independently hydrogen, C₁-C₂₀ alkyl, or C₆-C₂₀aryl;

R^(d) may be hydrogen or heavy hydrogen; and

R^(a) to R^(c) may not be simultaneously hydrogen.

The α-silyloxy-(Z)-alkenyl silane derivative of Chemical Formula 24 maybe prepared via a reaction between a furan compound represented byChemical Formula 22-1 and a silane compound of Chemical Formula A in thepresence of a borane catalyst.

In Chemical Formulae 22-1 and A,

R may be C₁-C₂₀ alkyl, C₆-C₂₀ aryl, or C₆-C₂₀ aryl C₁-C₂₀ alkyl, andalkyl, aryl, or arylalkyl of R may be further substituted with one ormore selected from the group consisting of halogen, C₁-C₂₀ alkyl, haloC₁-C₂₀ alkyl, C₁-C₂₀ alkoxy, C₆-C₂₀ aryl, C₆-C₂₀ aryloxy, and C₁-C₂₀alkylthio; and

R₁₁ to R₁₃ may each independently C₁-C₂₀ alkyl or C₆-C₂₀ aryl.

The borane catalyst may be, for example, B(C₆F₅)₃, (C₆F₅CH₂CH₂)B(C₆F₅)₂,(CF₃(CF₂)₃(CH₂)₂B(C₆F₅)₂, and HB(C₆F₅)₂, and B(C₆H₅)₃ and may be used in0.5 to 2.0 mol % based on 1 mol of a furan compound of Chemical Formula2-1.

The α-silyloxy-(Z)-alkenyl silane derivative of Chemical Formula 24 maybe, for example, the following compounds but is not limited thereto.

As the second aspect (II-2), the present invention may provide ananti-(2-alkyl)cyclopropyl silane derivative of Chemical Formula 21-2 viaa reaction between a furan compound of Chemical Formula 22-2 and thesilane compound of Chemical Formula 23 in the presence of a boranecatalyst.

In Chemical Formulae 21-2, 22-2, and 23,

L¹ may be C₆-C₂₀ arylene, and the arylene may be further substitutedwith one or more selected from the group consisting of halogen, C₁-C₂₀alkyl, halo C₁-C₂₀ alkyl, C₁-C₂₀ alkoxy, C₆-C₂₀ aryl, C₆-C₂₀ aryloxy,and C₁-C₂₀ alkylthio;

R^(a) to R^(c) may each independently hydrogen, C₁-C₂₀ alkyl, or C₆-C₂₀aryl;

R^(d) may be hydrogen or heavy hydrogen; and

R^(a) to R^(c) may not be simultaneously hydrogen.

As the third aspect (II-3), the present invention may provide a methodof preparing an anti-(2-alkyl)cyclopropyl silane derivative of ChemicalFormula 21-3 via a reaction between a furan compound of Chemical Formula22-3 and a silane compound of Chemical Formula 23 in the presence of aborane catalyst.

In Chemical Formulae 21-3, 22-3, and 23,

L² may be C₆-C₂₀ arylene;

R^(a) to R^(c) may each independently hydrogen, C₁-C₂₀ alkyl, or C₆-C₂₀aryl;

R^(d) may be hydrogen or heavy hydrogen; and

R^(a) to R^(c) may not be simultaneously hydrogen.

The method of preparing the anti-(2-alkyl)cyclopropyl silane derivativeaccording to the present invention may be a very effective method toobtain an anti-(2-alkyl)cyclopropyl silane derivative represented byChemical Formulae 21-1 to 21-3 in one pot with a high yield under a mildcondition via a reaction between a furan derivative represented byChemical Formulae 22-1 to 22-2 and a silane compound represented byChemical Formula 23 in the presence of a borane catalyst. In addition,the method of preparing the anti-(2-alkyl)cyclopropyl silane derivativeaccording to the present invention may prepare ananti-(2-alkyl)cyclopropyl silane derivative with a high yield via highstereoselectivity.

The method of preparing the anti-(2-alkyl)cyclopropyl silane derivativeaccording to the present invention may include two operations ofpreparing an α-silyloxy-(Z)-alkenyl silane derivative of ChemicalFormula 24 via a reaction between a furan compound of Chemical Formula22-1 and a silane compound of Chemical Formula A in the presence of aborane catalyst; and preparing an anti-(2-alkyl)cyclopropyl silanederivative of Chemical Formula 21-1 via a reaction between anα-silyloxy-(Z)-alkenyl silane derivative of Chemical Formula 24 and asilane compound of Chemical Formula 23 in the presence of a boranecatalyst and, in this case, the anti-(2-alkyl)cyclopropyl silanederivative may also be prepared with a high yield via highstereoselectivity.

The borane catalyst according to an embodiment of the aspect II of thepresent invention may be B(C₆F₅)₃ or B(C₆F₅)₂R³¹, R³¹ may be hydrogen,halogen, C₁-C₁₀ alkyl, or C₁-C₁₂ aryl, and alkyl or aryl of R³¹ may befurther substituted with halo C₁-C₁₀ alkyl or halo C₆-C₁₂ aryl. Anexample thereof may include B(C₆F₅)₃, (C₆F₅CH₂CH₂)B(C₆F₅)₂;(CF₃(CF₂)₃(CH₂)₂B(C₆F₅)₂, and HB(C₆F₅)₂, but may be easily handled dueto stability in the air, and may be B(C₆F₅)₃ in terms of reactionefficiency.

The borane catalyst according to an embodiment of the aspect II of thepresent invention may be used in 3.0 to 7.0 mol %, in detail, 3.0 to 5.0mol % based on 1 mol of furan compound of Chemical Formula 22-1 or anα-silyloxy-(Z)-alkenyl silane derivative of Chemical Formula 24 and,when the borane catalyst is used in this range, high product selectivityand a high yield may be obtained.

The borane catalyst according to an embodiment of the aspect II of thepresent invention may be used in 7.0 to 14.0 mol %, in detail, 9.5 to10.5 mol % based on 1 mol of a furan compound of Chemical Formula 22-2and, when the borane catalyst is used in this range, high productselectivity and a high yield may be obtained.

The borane catalyst according to an embodiment of the aspect II of thepresent invention may be used in 14.0 to 25.0 mol %, in detail, 19.0 to21.0 mol % based on 1 mol of a furan compound. of Chemical Formula 22-3and, when the borane catalyst is used in this range, high productselectivity and a high yield may be obtained.

In the silane compound of Chemical Formula 23 according to an embodimentof the aspect II of the present invention, R^(a) to R^(c) may eachindependently hydrogen, C₁-C₂₀ alkyl, or C₆-C₂₀ aryl, but, in detail,one or more of R^(a) to R^(c) may be C₁-C₂₀ alkyl or aryl. That is,R^(a) and R^(b) may each independently C₁-C₂₀ alkyl, R^(c) may behydrogen, or C₆-C₂₀ aryl, or R^(a) and R^(b) may each independentlyC₆-C₂₀ aryl, and R^(c) may be hydrogen in terms of reaction efficiency.For example, a silane compound of Chemical Formula 23 may be PhMe₂SiH,Ph₂SiH₂, Et₂SiH₂, or the like.

The silane compound according to an embodiment of the aspect IIaccording to the present invention may be used in 1 to 5 moles based on1 mol of a furan compound of Chemical Formula 22-1 or anα-silyloxy-(Z)-alkenyl silane derivative of Chemical Formula 24 and, inmore detail, may be used in 3 to 4 moles based on 1 mol of a furancompound of Chemical Formula 22-1 and may be used in 1 to 2 moles basedon 1 mol of an α-silyloxy-(Z)-alkenyl silane derivative of ChemicalFormula 24. When the silane compound is used in this range, reactionspeed may be high and a high yield may be obtained and, when the silanecompound is out of the range, there may be a problem in that a yield ofa product may be degraded or the remaining silane needs to beuneconomically discarded.

The silane compound according to an embodiment of the aspect IIaccording to the present invention may be used in 2 to 10 moles, indetail, 6 to 10 moles, in more detail, 7 to 9 moles based on 1 mol of afuran compound of Chemical Formula 22-2 and, in this case, when thesilane compound is used in this range, reaction speed may be high and ahigh yield may be obtained and, when the silane compound is outside therange, there may be a problem in that a yield of a product may bedegraded or the remaining silane needs to be uneconomically discarded.

The silane compound according to an embodiment of the aspect IIaccording to the present invention may be used in 3 to 15 moles, indetail, 10 to 15 moles, in more detail, 11 to 13 moles based on 1 mol ofa furan compound of Chemical Formula 22-3 and, when the silane compoundis outside the range, there may be a problem in that a yield of aproduct may be degraded or the remaining silane needs to beuneconomically discarded.

According to an embodiment of the aspect II of the present invention,the reaction may be performed in an organic solvent and, the organicsolvent may not be necessarily limited as long as the organic solventdoes not react with the borane catalyst and the silane compound. Anexample of the organic solvent may be chloroform, dichloromethane,toluene, chlorobenzene, benzene, hexane, dichloroethane, or a mixturesolvent thereof and may be dichloromethane in consideration of reactionefficiency as well as solubility of a reactant and ease of reactantremoval.

Reaction temperature of silylation reduction reaction according to anembodiment of the aspect II according to the present invention may beany general temperature used in organic synthesis, but may be changeddepending on a reaction time, a reaction material, and the amount of astart material, and the reaction may be performed at a temperature rangeof −78° C. to 50° C. to prevent a reaction time from being excessivelyincreased or to prevent a side reaction from occurring to prevent areduction in a reaction yield. In detail, reactants may be mixed at −78°C. to 0° C. and, then, the reaction may be performed at 20 to 50° C.

The reaction time according to an embodiment of the aspect II accordingto the present invention may be changed depending on a reactionmaterial, an amount of the reaction material, a type of a solvent, andan amount of the solvent, but a reaction may be performed for 4 to 24hours. After the reaction time elapses, the reaction time may beexcessively increased and a side reaction may occur to degrade areaction yield.

When the reaction is completed, a solvent may be distilled in a reducedpressure and, then, a target material may be isolated and purified via ageneral method such as column chromatography and re-crystallization.

The method of preparing as anti-(2-alkyl)cyclopropyl silane derivativeaccording to the present invention may be a very effective method thatuses a simple and relatively inexpensive borane catalyst that does notinclude metal under a very mild condition and uses a commerciallyavailable silane compound as a reducer and, thus, may performring-opening, hydrosilylation, and ring-closing on various furanderivatives generated from biomass to effectively synthesize ananti-(2-alkyl)cyclopropyl silane derivative which is relativelydifficult to synthesize with a short step as a basic synthesis unit ofmedicines and agricultural chemical products.

The present invention may provide an anti-(2-alkyl)cyclopropyl silanederivative represented by Chemical Formulae 21-1 to 21-3.

In Chemical Formulae 21-1 to 21-3,

R may be C₁-C₂₀ alkyl, C₆-C₂₀ aryl, or C₆-C₂₀ aryl C₁-C₂₀ alkyl, andalkyl, aryl, or arylalkyl of R may be further substituted with one ormore selected from the group consisting of halogen, C₁-C₂₀ alkyl, haloC₁-C₂₀ alkyl, C₁-C₂₀ alkoxy, C₆-C₂₀ aryl, C₆-C₂₀ aryloxy, and C₁-C₂₀alkylthio;

L¹ may be C₆-C₂₀ arylene, and the arylene may be further substitutedwith one or more selected from the group consisting of halogen,(C1-C20)alkyl, halo(C1-C20)alkyl, C₁-C₂₀ alkoxy, C₆-C₂₀ aryl, C₆-C₂₀aryloxy, and C₁-C₂₀ alkylthio;

L² may be C₆-C₂₀ arylene;

R^(a) to R^(c) may each independently hydrogen, C₁-C₂₀ alkyl, or C₆-C₂₀aryl;

R^(d) may be hydrogen or heavy hydrogen; and

R^(a) to R^(c) may not be simultaneously hydrogen.

The anti-(2-alkyl)cyclopropyl silane derivative prepared using thepreparation method according to the present invention may be, in detail,the following compounds but is not limited thereto.

Advantageous Effects

A method of preparing a silane derivative according to the presentinvention may use a borane catalyst instead of a transition metalliccatalyst and, thus, may be eco-friendly and, in particular, may easilyprepare a raw material and an intermediate in various fields with a highadded value due to use of a furan derivative derived from biomass as astart material and may be very economical.

The method of preparing a silane derivative according to the presentinvention may prepare a silane derivative with a high yield via highstereoselectivity under a mild condition and, thus, the silanederivative may be commercially mass-produced.

The silane derivative according to the present invention may be easilyused as an intermediate and a raw material in various fields, such asmedicines, industrial chemistry, and fine chemistry.

In detail, unlike a conventional method that requires use of toughreaction conditions and an expensive metallic catalyst, the method ofpreparing a silane derivative according to the present invention may usea simple and relatively inexpensive borane catalyst that does notinclude metal under a very mild condition and may use a commerciallyavailable silane compound as a reducer and, thus, may performring-opening, hydrosilylation, and ring-closing on various furanderivatives generated from biomass to effectively synthesize a silanederivative which is relatively difficult to synthesize with a short stepas a basic synthesis unit of medicines and agricultural chemicalproducts and may be mass-produced to achieve high probability of beingcommercially available.

The silane derivative obtained according to the present invent ion mayhave a silyl group and, thus, may be used to prepare a correspondingalcohol compound via an oxidation process and, in addition, the obtainedcorresponding alcohol compound may be further substituted with anotherfunctional group via a well known chemical reaction.

Accordingly, the silane derivative prepared using the preparation methodaccording to the present invention may be very usefully applied as anintermediate and a synthon of various fields, such as alkaloid,medicines, and agricultural chemical products.

The method of preparing a silane derivative according to the presentinvention may prepare various silane derivatives that are available as amedial and commercial raw material and intermediate from a furancompound derived from biomass with a high yield via highstereoselectivity under a mild condition, thereby enhancing an addedvalue of a biomass-derived material.

BEST MODE

Reference will now be made in detail to the exemplary embodiments of thepresent invention, but the following exemplary embodiments are given forbetter understanding of the present invention and the scope of thepresent invention is not limited thereto.

A furan derivative is synthesized and used using Preparation Examples 1and 2 below.

Preparation Example 1 General Method of Preparing Furan Derivative

Aryl bromide or aryl iodide (1.0 equiv), boronic acid (1.1 to 1.5equiv.), Pd(PPh₃)₄ (5 to 10 mol %), and Cs₂CO₃ (1.1 to 1.4 equiv.) wereput in a round bottom flask, toluene (content corresponding to 0.086 Mof arylhalide) and methanol (content corresponding to 0.33 M ofarylhalide) were added thereto, and the resultant was subjected to areaction at 100 to 110° C. for 12 hours. When the reaction wascompleted, the reaction mixture was cooled to 23° C., was quenched witha saturated NH₄Cl solution, and was subjected to extraction with ethylacetate (20 mL×3) and, then, an organic layer was washed with salt water(20 mL×1). The collected organic layers were dried with MgSO₄, weresubjected to vacuum evaporation, and were isolated and purified viasilica gel column chromatography to obtain a target compound.

2-[4-(Trifluoromethyl)phenyl]furan 84%).

Prepared from 1-bromo-4-(trifluoromethyl)benzene; colorless solid; m.p.90-92° C.; ¹H NMR (600 MHz,CDCl₃): δ 7.90-7.73 (m, 2H), 7.73-7.61 (m,2H), 7.53 (s, 1H), 6.80 (s, 1H), 6.53 (s, 1H); ¹³C NMR (100 MHz, CDCl₃):δ 152.7, 143.2, 134.1, 129.2 (q, J=32.3 Hz), 128.9, 128.6, 125.9, 124.3(q, J=272 Hz), 122.9, 112.1, 107.1; ¹⁹F NMR (3751 MHz, CDCl₃): δ −62.5;HRMS (EI): Calculated for C11H7F3O [M]+: 212.0449, Found: 212.0447.

2-(4-Fluorophenyl)furan (84%).

Prepared from 1-bromo-4-fluorobenzene; colorless solid; m.p. 32-34° C.;¹H NMR (600 MHz,CDCl₃): δ 7.73-7.58 (m, 2H), 7.54-77.40 (m, 1H), 7.09(t, J=8.7 Hz, 2H), 6.59 (d, J=3.4 Hz, 1H), 6.48 (dd, J=3.3,1.8 Hz, 1H);¹³C NMR (150 MHz, CDCl₃): δ 162.3 (d, J=246.8 Hz), 153.3, 142.1, 127.4(d, 3.2 Hz), 125.7 (d, J=8.0 Hz), 115.8 (d, J=21.9 Hz), 111.8, 104.8;¹⁹F NMR (565 MHz, CDCl₃): δ −114.4; HRMS (EI): Calculated for C10H7FO[M]+: 162.0481, Found: 162.0483.

2-(4-Chlorophenyl)furan (90%).

Prepared from 1-bromo-4-chlorobenzene; colorless solid; m.p. 64-66° C.;¹H NMR (600 MHz,CDCl₃): δ 7.65-7.58 (m, 2H), 7.47 (d, J=1.9 Hz, 1H),7.41-7.27 (m, 2H), 6.64 (d, J==3.4 Hz, 1H), 6.48 (dd, J=3.5, 1.8 Hz,1H); ¹³C NMR (150 MHz, CDCl₃): δ 153.1, 142.5, 133.1, 129.5, 129.0,125.2, 111.9, 105.6; HRMS (EI): Calculated for C10H7ClO [M]+: 178.0185,Found: 178.0186.

2-(4-Bromophenyl)furan (52%).

Prepared from 1,4-dibromobenzene; colorless solid; m.p. 75-77° C.; ¹HNMR (600 MHz,CDCl₃): δ 7.54 (d, J=8.5 Hz, 2H), 7.50 (d, J=8.5 Hz, 2H),7.47 (s, 1H), 6.66 (s, 1H), 6.47 (s, 1H); ¹³C NMR (150 MHz, CDCl₃): δ153.1, 142.5, 131.9, 129.9, 125.4, 121.2, 111.9, 105.7; HRMS (EI):Calculated for C10H7BrO [M]+: 221.9680, Found: 221.9678.

2-(1,1′-Biphenyl-4-yl)furan (85%).

Prepared from 4-bromo-1,1′-biphenyl; colorless solid; m.p. 156-158° C.;¹H NMR (600 MHz,CDCl₃): δ 7.86-7.79 (m,2H), 7.73-7.70 (m, 2H), 7.71-7.68(m, 2H), 7.57 (dd, J=1.8, 0.8 Hz, 1H), 7.55-7.49 (m, 2H), 7.47-7.39 (m,1H), 6.76 (dd, J=3.3, 0.8 Hz, 1H), 6.57 (dd, J=3.4, 1.8 Hz, 1H); ¹³C NMR(150 MHz, CDCl₃): δ 153.8, 142.2, 140.6, 140.0, 129.9, 128.9, 127.42,127.41, 126.9, 124.3, 111.8, 105.2; HRMS (EI): Calculated for C16H12O[M]+: 220.0888, Found: 220.0890.

2-Phenylfuran (92%).

Prepared from 1-bromobenzene; colorless liquid; ¹H NMR (600 MHz,CDCl₃):δ 7.77-7.67 (m, 2H), 7.51 (d, J=1.8 Hz, 1H), 7.42 (t, J=7.8 Hz, 2H),7.30 (t, J=7.2, Hz, 1H), 6.69 (d, J=3.3 Hz, 1H), 6.51 (dd, J=3.4, 1.8Hz, 1H); ¹³C NMR (150 MHz, CDCl₃): δ 154.1, 142.2, 131.0, 128.8, 127.5,123.9, 111.8, 105.1

2-(m-Tolyl)furan (86%).

Prepared from 1-bromo-3-methylbenzene; colorless liquid; ¹H NMR (600MHz,CDCl₃): δ 7.57-7.45 (m, 3H), 7.29 (s, 1H), 7.09 (d, J=7.9 Hz,1H),6.65 (d, J=3.0 Hz, 1H), 6.48 (d, J=1.7 Hz, 1H), 2.40 (s, 3H); ¹³C NMR(150 MHz, CDCl₃): δ 154.1, 141.9, 138.2, 130.8, 128.5, 128.1, 124.4,120.9, 111.5, 104.8, 21.5

2-(4-Phenoxyphenyl)furan (91%).

Prepared from 1-bromo-4-phenoxybenzene; colorless solid; m.p. 63-65° C.;¹H NMR (600 MHz,CDCl₃): δ 7.65 (d, J=8.4 Hz, 2H), 7.46 (s, 1H), 7.36 (t,J=7.7 Hz, 2H), 7.13 (t, J=7.4 Hz, 1H), 7.04 (dd, J=8.2, 5.8 Hz, 4H),6.59 (s, 1H), 6.48 (s, 1H); ¹³C NMR (150 MHz, CDCl₃): δ 157.2, 156.8,153.8, 141.9, 129.9, 126.5, 125.5, 123.5, 119.2, 119.1, 111.8, 104.4;HRMS (EI): Calculated for C16H12O2 [M]+: 236.0837, Found: 236.0835.

2-[4-(Methylthio)phenyl]furan 83%).

Prepared from (4-bromophenyl)(methyl)sulfane; brown color solid; m.p.79-81° C.; ¹H NMR (600 MHz,CDCl₃): δ 7.63 (d, J=8.2, Hz, 2H), 7.48-7.40(m, 1H), 7.26 (d, J=8.4 Hz, 2H), 6.60 (t, J=3.3 Hz, 1H), 6.48-6.42 (m,1H), 2.49 (s, 3H); ¹³C NMR (150 MHz, CDCl₃): δ 153.6, 141.8, 137.5,127.9, 126.8, 124.2, 111.6, 104.6, 15.8; HRMS (EI): Calculated forC11H10OS [M]+: 190.0452, Found: 190.0452.

Preparation Example 2 General Method of Preparing Furanyl AlcoholDerivative Protected with Silyl Group

CH₂Cl₂ (5 mL) was put in a dried flask, alcohol (1.0 equiv.) synthesizedand prepared at 0° C. using the same way as in Preparation Example 1 wasadded thereto, imidazole (1.3 equiv.) was slowly added thereto at thesame temperature and, then, was stirred for 10 minutes, silyl chloride(1.2 equiv.) melted in CH₂Cl₂ (10 mL) was added thereto, and theresultant was subjected to a reaction at 23° C. for 12 hours. Thereaction mixture was quenched with a saturated NH₄Cl solution, and wassubjected to extraction with ethyl acetate (20 mL×3) and, then, anorganic layer was washed with salt water (10 mL×1). The collectedorganic layers were dried anhydrous Na₂SO₄, were subjected to vacuumevaporation, and were isolated and purified via column chromatography toobtain a target compound.

[4-(Furan-2-yl)phenoxy]triisopropylsilane (76%)

Prepared from 4-iodophenol; colorless liquid; ¹H NMR (600 MHz,CDCl₃): δ7.61-7.52 (m, 2H), 7.43 (d, J=2.0 Hz, 1H), 7.01-6.88 (m, 2H), 6.52 (d,J=3.4 Hz, 1H.), 6.45 (dd, J=3.4, 1.8 Hz, 1H), 1.34-1.25 (m, 3H), 1.14(d, J=7.4 Hz, 18H); ¹³C NMR (150 MHz, CDCl₃): δ 155.8, 154.3, 141.5,125.3, 124.5, 120.3, 111.7, 103.5, 18.1, 12.9; 29Si NMR (120 MHz,CDCl3): δ 15.7; HRMS (EI): Calculated for C19H28O2Si [M]+: 316.1859,Found: 316.1858.

2-(3,5-Dibromophenyl)furan (56%)

Prepared from 1,3,5-tribromobenzene; colorless solid; m.p. 44-46° C.; ¹HNMR (600 MHz,CDCl₃): δ 7.72 (t, J=1.6 Hz, 2H), 7.52 (d, J=1.8 Hz, 1H),7.47 (s, 1H), 6.68 (dd, J=3.2, 1.6 Hz, 1H), 6.52-6.42 (m, 1H); ¹³C NMR(150 MHz, CDCl₃): δ 150.8, 143.2, 133.9, 132.3, 125.3, 123.24, 111.9,107.1; HRMS (EI): Calculated for C10H6Br2O [M]+: 299.8785, Found:299.8786.

2-(2,4,6-Triisopropylphenyl)furan (28%)

Prepared from 2-bromo-1,3,5-triisopropylbenzene; colorless solid; m.p.103-105° C.; ¹H NMR (600 MHz,CDCl₃): δ 7.53 (d, J=1.9 Hz, 1H), 7.10 (s,2H), 6.76-6.45 (m, 1H), 6.29 (d, J=3.2 Hz, 1H), 3.06-2.88 (m, 1H),2.80-2.63 (m, 2H), 1.33 (d, J=6.9 Hz, 6H), 1.19 (d, J=6.9 Hz, 12H); ¹³CNMR (150 MHz, CDCl₃): δ 152.3, 150.2, 149.7, 141.6, 126.8, 120.8, 110.3,109.4, 34.6, 30.9, 24.4, 24.2; HRMS (EI): Calculated for C19H26O [M]+:270.1984, Found: 270.1982.

2-(Phenanthren-9-yl)furan (79%)

Prepared from 9-bromophenanthrene; colorless solid; m.p. 86-88° C.; ¹HNMR (600 MHz,CDCl₃): δ 8.87-8.78 (m, 1H), 8.76-8.70 (m, 1H), 8.66-857(m, 1H), 8.15 (d, J=3.4 Hz, 1H), 8.00 (dd, J=7.9, 3.4 Hz, 1H), 7.82-7.65(m, 5H), 6.91 (s, 1H), 6.73 (s, 1H); ¹³C NMR (150 MHz, CDCl₃): δ 153.5,142.5, 131.4, 130.9, 130.3, 129.7, 129.0, 127.5, 127.4, 127.1, 126.9,126.9, 126.7, 126.4, 123.1, 122.6, 111.5, 109.7; HRMS (EI): Calculatedfor C8H12O [M]+: 244.0888, Found: 244.0887.

1,4-Di(furan-2-yl)benzene (13%).

Prepared from 1,4-dibromobenzene; yellow color solid; m.p. 135-140° C.;¹H NMR (600 MHz,CDCl₃): δ 7.83-7.61 (m, 4H), 7.47 (d, J=1.8 Hz, 2H),6.66 (d, J=3.3 Hz, 2H), 6.48 (dd, J=3.4, 1.8 Hz, 2H); ¹³C NMR (150 MHz,CDCl₃): δ 153.9, 142.3, 129.9, 124.2, 111.9, 105.3; HRMS (EI):Calculated for C14H10O2 [M]+: 210.0681, Found: 210.0677.

2,2′-(5-Bromo-1,3-phenylene)difuran (8%)

Prepared from 1,3,5-tribromobenzene; colorless solid; m.p. 77-79° C.; ¹HNMR (600 MHz,CDCl₃): δ 7.86 (d, J=2.0 Hz, 1H), 7.67 (t, J=1.7 Hz, 2H),7.49 (d, J=2.6 Hz, 2H), 6.71 (t, J=2.7 Hz, 2H), 6.49 (dt, J=3.4, 1.8 Hz,2H); 13C NMR (150 MHz, CDCl3): δ 152.1, 142.7, 132.9, 125.2, 123.1,117.5, 111.8, 106.4.

1,3,5-Tri(furan-2-yl)benzene (81%)

Prepared from 1,3,5-tribromo-benzene; colorless solid; m.p. 138-140° C.;¹H NMR (600 MHz,CDCl₃): δ 7.90 (s, 3H), 7.53 (d, J=2.3 Hz, 3H), 6.78 (d,J=3.2 Hz, 3H), 6.52(dd, J=3.5, 1.8 Hz, 3H); ¹³C NMR (150 MHz, CDCl₃): δ153.4, 142.3, 131.6, 118.0, 111.7, 105.7; HRMS (EI): Calculated forC18H12O3 [M]+: 276.0786, Found: 276.0787.

3-[4-(tert-Butyl)phenyl]furan (68%)

Prepared from 3-bromofuran; colorless solid; m.p. 59-61° C.; ¹H NMR (600MHz,CDCl₃): δ 7.73 (s, 1H), 7.49 (s, 1H), 7.44 (q, J=7.9 Hz, 4H), 6.72(s, 1H), 1.37 (s, 9H); ¹³C NMR (150 MHz, CDCl₃): δ 150.1, 143.6, 138.4,129.7, 126.4, 125.8, 125.8, 109.1, 34.7, 31.5; HRMS (EI): Calculated forC14H16O [M]+: 200.1201, Found: 200.1199.

[4-(Benzofuran-2-yl)phenoxy]triisopropylsilane (83%).

Prepared from 4-iodophenol; colorless solid; m.p. 46-48° C.; ¹H NMR (600MHz,CDCl₃): δ 7.74 (d, J=8.7 Hz, 2H), 7.55 (d, J=6.9 Hz, 1H), 7.50 (d,J=8.1 Hz, 1H), 7.33-7.17 (m, 2H), 6.96 (d, J=8.7 Hz, 2H), 6.88 (s, 1H),1.41-1.20 (m, 3H), 1.14 (d, 9H), 1.14 (d, 9H); ¹³C NMR (150 MHz, CDCl₃):δ 156.9, 156.3, 154.9, 129.7, 126.5, 123.8, 123.8, 122.9, 120.7, 120.4,111.1, 99.8, 18.1, 12.9; ²⁹Si NMR (120 MHz, CDCl₃): δ 16.1; HRMS (EI):Calculated for C23H30O2Si [M]+: 366.2015, Found: 366.2018.

2-Phenylbenzofuran (89%)

Prepared from 1-bromobenzene; colorless liquid; ¹H NMR (600 MHz,CDCl₃):δ 7.97 (d, J=7.2 Hz, 2H), 7.68 (d, J=8.1 Hz, 1H), 7.63 (d, J=8.7 Hz,1H), 7.55 (t, J=7.7 Hz, 2H), 7.45 (t, J=6.3 Hz, 1H), 7.38 (t, J=7.7 Hz,1H), 7.36-7.30 (m, 1H), 7.12 (s, 1H); ¹³C NMR (150 MHz, CDCl₃): δ 156.1,155.1, 130.7, 129.4, 128.9, 128.7, 125.1, 124.4, 123.1, 121.0, 111.3,101.5; HRMS (EI): Calculated for C14H10O [M]+: 194.0732, Found:194.0730.

2-[(1,1′-Biphenyl)-4-ylmethyl]furan (92%)

Prepared from 4-(bromomethyl)-1,1′-biphenyl; colorless solid; m.p.81-83° C.; ¹H NMR (600 MHz,CDCl₃) δ 7.60 (d, J=7.8 Hz, 2H), 7.56 (d,J=8.0 Hz, 2H), 7.45 (t, J=7.6 Hz, 2H), 7.37 (s, 1H), 7.36-7.31 (m, 3H),6.34 (s, 1H), 6.08 (s, 1H), 4.04 (s, 2H); ¹³C NMR (150 MHz, CDCl₃) δ154.6, 141.7, 141.1, 139.6, 137.4, 129.2, 128.9, 127.4, 127.3, 127.2,110.4, 106.5, 34.3; HRMS (EST): Calculated for C17H14ONa [M+Na]+:257.0942, Found: 257.0911.

A silane derivative was synthesized according to the following exemplaryembodiments using the furan derivatives prepared in Preparation Examples1 and 2 above.

I. Preparation of Silyloxyalkenyl Silane Derivative Inventive Example 1General Preparation of (Z)-α-silyloxyalkenylsilane (DerivativeSilyloxyalkenylsilanes)

CH₂Cl₂ (0.4-0.8 mL) and B(C₆F₅)₃ (0.01 to 0.02 mmol, 2.0 mol %) were putin a dried flask, a silane compound (PhMe₂SiH, 1.025 to 2.050 mmol) wasadded thereto and was well stirred and, then, a furan derivative (0.50to 1.0 mmol) was again added thereto and, then, was stirred at 23° C.for 1 to 5 hours. The reaction mixture was quenched with Et3N (5.0 to10.0 mol %), was subjected to vacuum evaporation, and was isolated andpurified (to nucleic acid or hexane and ethyl acetate) via silica gelcolumn chromatography to obtain a target product (Z/E>99/1).

The following compound was prepared using the same method as the above.

(Z)-[1-(Dimethylphenylsilyloxy)pent-3-en-1-yl]dimethylphenylsilane(95%). The compound was prepared by stirring 2-methylfuran (3.284 g, 40mmol) and dimethylphenylsilane (11.18 g, 82 mmol) at 23° C. for 12 hoursin the presence of B(C₆F₅)₃ (409.6 mg, 2.0 mol %) melted in CH₂C₁₂ (8mL) under argon gas, and had a conversion yield of >95% from analysisvia ¹H NMR. Yield of 91% (12.88 g);

colorless liquid; ¹H NMR (600 MHz, CDCl3): δ 7.66-7.57 (m, 4H),7.50-67.38 (m, 6H), 5.52-5.40 (m, 2H), 3.75 (t, J=6.9 Hz, 1H), 2.44-2.30(m, 2H), 1.56 (dd, J=6.6, 1.6 Hz, 3H), 0.39 (s, 6H), 0.36 (s, 3H), 0.35(s, 3H); ¹³C NMR (100 MHz, CDCl₃): δ 138.8, 137.8, 134.4, 133.8, 129.4,129.1, 128.4, 127.7 (2C), 125.1, 66.9, 32.0, 13.0, −0.8, −0.9, −4.5,−4.7; ²⁹Si NMR (120 MHz, CDCl₃): δ 6.0, −4.2; HRMS (EI): Calculated forC21H30OSi2 [M]+: 354.1835, Found: 354.1831.

(Z)-1-(Dimethylphenylsilyl)hex-3-en-1-ol (86%). (i) Preparation wasperformed via a reaction between dimethylphenylsilane (279 mg, 2.1 mmol)and 2-ethylfuran (96 mg, 1.0 mmol) at 23° C. for 1.5 hours in thepresence of B(C₆F₅)₃ (10.2 mg, 2.0 mol %) melted in CH₂Cl₂ (0.8 ml)under argon gas. After the reaction was completed, K₂CO₃ (276 mg, 2.00mmol) obtained by melting the reaction mixture in MeOH (2 mL) was addedand was subjected to a reaction at 23° C. for 4 hours (201.5 mg, 86% fortwo steps).

colorless liquid; ¹H NMR (600 MHz, CDCl₃): δ 7.70-7.57 (m, 2H),7.48-7.30 (m, 3H), 5.97-5.57 (m, 1H), 5.45-5.10 (m, 1H), 3.50 (d, J=10.6Hz, 1H), 2.40 (q, J=12 Hz, 1H), 2.28-2.17 (m, 1H), 2.07 (d, J=6.7 Hz,2H), 1.56 (brs, 1H), 0.99 (t, J=6.7 Hz, 3H), 0.42 (s, 3H), 0.41 (s, 3H);¹³C NMR (150 MHz, CDCl₃): δ 136.9, 135.3, 134.2, 129.3, 127.9, 125.9,64.5, 31.4, 20.7, 14.4, −5.3, 5.5; ²⁹Si NMR (120 MHz, CDCl₃): δ −3.8;HRMS (EI): Calculated for C14H22OSi [M]+: 234.1440, Found 234.1440.

(Z)-[1-(Dimethylphenylsilyloxy)hept-3-en-1-yl]dimethylphenylsilane(92%). The compound was prepared from 2-propylfuran.;

colorless liquid; ¹H NMR (600 MHz, CDCl₃): δ 7.60-7.51 (m, 4H),7.32-7.42 (m, 6H), 5.56-5.17 (m, 2H), 3.66 (t, J=6.9 Hz, 1H), 2.67-2.23(m, 2H), 1.87 (q, J=6.6 Hz, 2H), 1.37-1.26 (m, 2H), 0.87 (t, J=7.4 Hz,3H), 0.32 (s, 6H), 0.29 (s, 3H), 0.28 (s, 3H); ¹³C NMR (150 MHz, CDCl₃):δ 138.8, 137.8, 134.4, 133.8, 131.0, 129.4, 129.1, 127.7 (2C), 127.5,67.1, 32.4, 29.5, 22.9, 13.9, −0.7, −0.9, −4.5, −4.7; ²⁹Si NMR (120 MHz,CDCl₃): δ 5.9, −4.3; HRMS (EI): Calculated for C23H34OSi2 [M]+:383.2148, Found: 382.2144.

(Z)-1-[(Dimethylphenylsilyloxy)-non-3-en-1-yl]dimethylphenylsilane(reaction time: 1 h, 86%). The compound was prepared from 2-pentylfuran.

colorless liquid; ¹H NMR (600 MHz, CDCl₃): δ 7.57-7.48 (m, 4H),7.42-7.31 (m, 6H), 5.41-5.12 (m, 2H), 3.65 (t, J=6.9 Hz, 1H), 2.34-2.23(m, 2H), 1.94-1.82 (m, 2H), 1.33-1.26 (m, 4H), 1.26-1.17 (m, 2H), 0.90(t, J=7.1 Hz, 3H), 0.31 (s, 6H),0.28 (s, 3H), 0.27 (s, 3H); ¹³C NMR (150MHz, CDCl₃): δ 138.8, 137.8, 134.4, 133.79, 131.3, 129.4, 129.1, 127.7(2C), 127.3, 67.1, 32.4, 31.70, 29.4, 27.5, 22.7, 14.2, −0.7, −0.9,−4.5, −4.7; ²⁹Si NMR (120 MHz, CDCl₃): δ 5.9, −4.3; HRMS (ESI):Calculated for C25H38ONaSi2 [M+Na]+: 433.2359, Found: 433.2368.

(Z)-1-[(Dimethylphenylsilyloxy)-4-(4-trifluoromethylphenyl)but-3-en-1-yl]dimethylphenylsilane(reaction time: 4 h, 90%). The compound was prepared from2-[4-(trifluoromethyl)phenyl]furan.

colorless liquid; ¹H NMR (600 MHz, CDCl₃): δ 7.62-7.57 (m, 1H), 7.54 (d,J=6.8 Hz, 2H), 7.52-7.46 (m, 3H), 7.41-7.34 (m, 5H),7.33-7.27 (m, 3H),6.39 (d, J=11.7 Hz, 1H), 5.75 (dt, J=11.7, 7.4 Hz, 1H), 3.77 (dd, J=8.0,5.2 Hz, 1H), 2.65-2.55 (m, 1H), 2.50-2.41 (m, 1H), 0.38(s, 3H), 0.31 (s,6H), 0.30 (s, 3H); ¹³C NMR (150 MHz, CDCl₃): δ 141.1, 138.4, 137.2,134.3, 133.8, 133.1, 129.6, 129.3, 129.0, 128.9, 127.8 (2C), 126.2,125.1 (q, J=4.5 Hz), 124.5 (q, J=273 Hz), 66.8, 33.2, −0.8, −0.9, −4.7,−4.9; ²⁹Si NMR (120 MHz, CDCl₃): δ 6.6, −4.0; ¹⁹F NMR (565 MHz, CDCl3) δ−1114.4; HRMS (ESI): Calculated for C27H31F3NaOSi2 [M+Na]+: 507.1763,Found: 507.1771.

(Z)-1-[(Dimethylphenylsilyloxy)-4-(4-fluorophenyl)but-3-en-1-yl]dimethylphenylsilane(reaction time: 1.5 h, 85%). The compound was prepared from2-(4-fluorophenyl)furan.

colorless liquid; ¹H NMR (600 MHz, CDCl₃): δ 7.53 (d, J=6.7 Hz, 2H),7.47 (d, J=7.2 Hz, 2H), 7.41-7.30 (m, 6H), 7.18-7.12 (m, 2H), 6.99-6.90(m,2H), 6.33 (d, J=11.6 Hz, 1H), 5.62 (dt, J=11.3, 7.3 Hz, 1H), 3.74(dd, J=7.9, 5.5 Hz, 1H), 2.58 (dt, J=15.6, 8.0 Hz, 1H), 2.45 (dt,J=15.1, 6.0 Hz, 1H), 0.30(s, 3H), 0.29 (s, 6H), 0.28 (s, 3H); ¹³C NMR(150 MHz, CDCl₃): δ 161.6 (d, J=246.0 Hz) 138.5, 137.4, 134.4, 133.8,133.6 (d, J=3.0 Hz), 133.1, 130.7, 130.4 (d, J=8.0 Hz), 129.5, 129.2,128.9, 127.8, 115.0 (d, J=21.0 Hz), 66.9, 33.1, −0.8, −0.9, −4.7, −4.9;²⁹Si NMR (120 MHz, CDCl3): δ 6.5, −4.1; ¹⁹F NMR (375 MHz, CD₂Cl₂): δ−115.9; HRMS (EI): Calculated for C26H31FOSi2 [M]+: 434.1897, Found:434.1901.

(Z)-1-[(Dimethylphenylsilyloxy)-4-(4-chlorophenyl)but-3-en-1-yl]dimethylphenylsilane(reaction time: 2 h, 86%). The compound was prepared from2-(4-chlorophenyl)furan.

colorless liquid; ¹H NMR (600 MHz, CDCl₃): δ 7.56-7.52 (m, 2H), 7.47 (d,J=7.2 Hz, 2H), 7.42-7.30 (m, 6H), 7.23 (d, J=8.1 Hz, 2H), 7.12 (d, J=8.2Hz, 2H), 6.32 (d, J=11.6 Hz, 1H), 5.65 (dt, J=11.7, 7.5 Hz, 1H), 3.75(dd, J=8.0, 5.5 Hz, 1H), 2.69-2.53 (m, 1H), 2.48-2.29 (m, 1H), 0.30 (s,9H),0.29 (s, 3H); ¹³C NMR (150 MHz, CDCl₃): δ 138.5, 137.3, 136.0,134.4, 133.8, 132.3, 131.5, 130.1, 129.5, 129.3, 128.9, 128.3, 127.80,127.78, 66.8, 33.2, −0.8, −0.9, −4.7, −4.9; ²⁹Si NMR (120 MHz, CDCl₃): δ6.5, −4.1; HRMS (EI): Calculated for C26H31ClOSi2 [M]+: 450.1602, Found:450.1600.

(Z)-1-[(Dimethylphenylsilyloxy)-4-(4-bromophenyl)but-3-en-1-yl]dimethylphenylsilane(reaction time: 2 h, 91%). The compound was prepared from2-(4-bromophenyl)furan.

Colorless liquid; ¹H NMR (600 MHz,CDCl₃): δ 7.53 (d, J=9.2 Hz, 2H), 7.47(d, J=7.9 Hz, 2H), 7.42-7.30 (m, 8H), 7.06 (d, J=8.3 Hz, 2H), 6.30 (d,J=11.7 Hz, 1H), 5.89-5.56 (m, 1H), 3.79-3.70 (m, 1H), 2.58 (dd, J=15.7,7.5 Hz, 1H), 2.51-2.36 (m, 1H), 0.30 (s, 6H), 0.30 (s, 3H), 0.29 (s,3H); ¹³C NMR (150 MHz, CDCl₃): δ 138.5, 137.3, 136.4, 134.3, 133.8,131.6, 131.2, 130.4, 129.5, 129.3, 128.9, 127.80, 127.78, 120.4, 66.8,33.1, −0.8, −0.9, −4.7, −4.9; ²⁹Si NMR (120 MHz, CDCl₃): δ 6.5, −4.1;HRMS (EI): Calculated for C26H31BrOSi2 [M]+: 494.1097, Found: 494.1092.

(Z)-{4-[(1,1′-Biphenyl)-4-yl]-1-(dimethylphenylsilyloxy)but-3-en-1-yldimethylphenylsilane (reaction time: 3 h, 92%). The compound wasprepared from 2-(1,1′-biphenyl-4-yl)furan.

colorless liquid; ¹H NMR (400 MHz, CDCl₃): δ 7.86-7.79 (m, 2H),7.79-7.74 (m, 2H), 7.73-7.67 (m, 4H), 7.64 (t, J=7.6 Hz, 2H),7.58-7.46(m, 9H), 6.63 (d, J=11.7 Hz, 1H), 5.95-5.81 (m, 1H), 4.00 (dd,J=7.8, 5.6 Hz, 1H), 2.98-2.84 (m, 1H), 2.84-2.70 (m, 1H), 0.53 (s, 3H),0.52 (s, 6H), 0.51 (s, 3H); ¹³C NMR (100 MHz, CDCl₃): δ 141.1, 139.36,138.6, 137.4, 136.7, 134.5, 133.9, 131.1, 129.7, 129.6, 129.4, 129.3,128.9, 127.9 (2C), 127.4, 127.1, 126.9, 67.1, 33.4, −0.6, −0.7, −4.6,−4.7; ²⁹Si NMR (80 MHz, CDCl₃): δ 6.6, −3.9; HRMS (ESI): Calculated forC32H36NaOSi2 [M+Na]+: 515.2202, Found: 515.2200.

(Z)-1-[(Dimethylphenylsilyloxy)-4-phenylbut-3-en-1-yl]dimethylphenylsilane(reaction time: 2 h, 91%). The compound was prepared from 2-phenylfuran.

colorless liquid; ¹H NMR (600 MHz, CDCl₃): δ 7.57 (d, J=9.2 Hz, 2H),7.51 (d, J=7.9 Hz, 2H), 7.43-7.48 (m, 4H), 7.37-7.29 (m, 4H), 7.26 (d,3H), 6.43 (d, J=11.7 Hz, 1H), 5.78-5.56 (m, 1H), 3.93-3.53 (m, 1H), 2.66(t, J=7.1 Hz, 1H), 2.61-2.39 (m,1H), 0.34 (s, 3H), 0.33 (s, 6H), 0.32(s, 3H); ¹³C NMR (150 MHz, CDCl₃): δ 138.6, 137.6, 137.5, 134.4, 133.8,133.1, 130.8, 130.1, 129.5, 129.2, 128.9, 128.2, 127.8, 126.6, 67.0,33.3, −0.8, −0.8, −4.8, −4.8; ²⁹Si NMR (120 MHz, CDCl₃): δ 6.5, −4.1.

(Z)-[1-(Dimethylphenylsilyloxy)-4-(m-tolyl)but-3-en-1-yl]dimethylphenylsilane(reaction time: 2 h, 83%). The compound was prepared from2-(m-tolyl)furan.

colorless liquid; ¹H NMR (600 MHz, CDCl₃): δ 7.59-7.46 (m, 4H),7.47-7.29 (m, 6H), 7.19 (t, J=7.6 Hz, 1H), 7.14-7.00 (m, 3H), 6.39 (d,J=11.6 Hz, 1H), 5.75-5.54 (m, 1H), 3.78 (t, J=6.8 Hz, 1H), 2.73-2.59 (m,1H), 2.59-2.47 (m, 1H), 2.35 (s, 3H), 0.31 (s, 12H); ¹³C NMR (150 MHz,CDCl₃): δ 138.5, 137.5, 137.4, 137.3, 134.3, 133.6, 130.5, 130.0, 129.5,129.3, 129.0, 127.9, 127.6 (2C), 127.2, 125.8, 66.9, 33.1, 21.4, −0.9(2C), −4.8, −4.9; ²⁹Si NMR (120 MHz, CDCl₃): δ=6.3, −4.1; HRMS (ESI):Calculated for C27H34NaOSi2 [M+Na]+: 453.2046, Found: 453.2040.

(Z)-1-[(Dimethylphenylsilyloxy)-4-(4-phenoxyphenyl)-but-3-en-1-yl]dimethylphenylsilane(reaction time: 1.5 h, 61%). The compound was prepared from2-(4-phenoxyphenyl)furan.

colorless liquid; ¹H NMR (600 MHz, CDCl₃): δ 7.62 (d, J=6.4 Hz, 2H),7.57(d, J=6.4 Hz, 2H), 7.48-7.37 (m, 8H), 7.25 (d, J=8.3 Hz, 2H), 7.20(t, J=7.4 Hz, 1H), 7.12 (d, J=8.5 Hz, 2H), 7.00 (d, J=8.4 Hz, 2H), 6.44(d, J=11.5 Hz, 1H), 5.71 (dt, J=11.5, 7.1 Hz, 1H), 3.85 (t, J=6.7 Hz,1H), 2.76-2.67 (m, 1H), 2.65-2.53 (m, 1H), 0.38 (s, 12H); ¹³C NMR (150MHz, CDCl₃): δ 157.4, 155.8, 138.5, 137.4, 134.4, 133.8, 132.8, 130.3,130.1, 129.8, 129.5, 129.3, 129.2, 127.8 (2C), 123.3, 118.9, 118.6,67.0, 33.2, −0.7, −0.8, −4.7, −4.8; ²⁹Si NMR (120 MHz, CDCl₃): δ 6.5,−4.1; HRMS (EI): Calculated for C32H36O2Si2 [M]+: 508.2254, Found:508.2256.

(Z)-1-[(Dimethylphenylsilyloxy)-4-(4-methylthiophenyl)-but-3-en-1-yl]dimethylphenylsilane(reaction time: 1.5 h, 91%).

colorless liquid; ¹H NMR (600 MHz, CDCl₃): δ 7.51 (d, J=7.6 Hz, 2H),7.46 (d, J=7.0 Hz, 2H), 7.40-7.27 (m, 6H), 7.19-7.09 (m, 4H), 6.30 (d,J=11.6 Hz, 1H), 5.59 (dt, J=12.1, 7.5 Hz, 1H), 3.73 (t, J=6.6 Hz, 1H),2.73-2.55 (m, 1H), 2.49 (s, 3H), 2.48-2.43 (m, 1H), 0.27 (s, 12 H); ¹³CNMR (150 MHz, CDCl₃): δ 138.6, 137.4, 136.4, 134.6, 134.4, 133.8, 130.7,129.5, 129.4, 129.3, 129.2, 127.8 (2C), 126.5, 66.9, 33.3, 16.1, −0.8,−0.9, −4.8, −4.8; ²⁹Si NMR (120 MHz, CDCl₃): δ 6.4, −4.1; HRMS (EI):Calculated for C27H34OSSi2 [M]+: 462.1869, Found: 462.1871.

(Z)-{1-[(Dimethylphenylsilyl)-4-(dimethylphenylsilyloxy)-but-1-en-1-yl]phenoxy)triisopropylsilane(reaction time: 3 h, 95%).

colorless liquid; ¹H NMR (600 MHz, CDCl₃): δ 7.54 (d, J=6.5 Hz, 2H),7.50 (d, J=6.5 Hz, 2H), 7.41-7.30 (m, 6H), 7.08 (d, J=8.4 Hz, 2H), 6.80(d, J=8.5 Hz, 2H), 6.32 (d, J=11.6 Hz, 1H), 5.61-5.45 (m, 1H), 3.79-3.73(m, 1H), 2.66-2.51 (m, 2H), 1.36-1.25 (m, 3H), 1.15 (d, J=7.4 Hz, 18H),0.29 (s, 12H); ¹³C NMR (150 MHz, CDCl₃): δ 154.8, 138.7, 137.6, 134.4,133.8, 130.6, 130.0, 129.6, 129.4, 129.2, 128.9, 127.7 (2C), 119.6,67.1, 33.3, 18.1, 12.9, −0.7, −0.8, −4.8, −4.8; ²⁹Si NMR (120 MHz,CDCl₃): δ 15.2, 6.3, −4.2; HRMS (EI): Calculated for C35H52O2Si3 [M]+:588.3275, Found: 588.3279.

(Z)-[4-(3,5-Dibromophenyl)-1-(dimethylphenylsilyloxy)but-3-en-1-yl]dimethylphenylsilane(reaction time: 15 h, 79%). The compound was prepared from2-(3,5-dibromophenyl)furan.

colorless liquid; ¹H NMR (600 MHz, CDCl₃): δ 7.54-7.49 (m, 3H),7.49-7.44(m, 2H), 7.43-7.28 (m, 8H), 6.21 (d, J=11.7 Hz, 1H), 5.72-5.67 (m, 1H),3.75 (dd, J=8.6, 4.9 Hz, 1H), 2.62-2.52 (m, 1H), 2.37-2.27 (m, 1H), 0.29(s, 6H), 0.28 (s, 6H); ¹³C NMR (150 MHz, CDCl₃): δ 140.8, 138.1, 136.9,134.1, 133.6, 133.6, 131.8, 130.3, 129.4, 129.2, 127.7, 127.6, 127.5,122.5, 66.4, 32.8, −1.0 (2C), −4.9, −5.0; ²⁹Si NMR (120 MHz, CDCl₃): δ6.7, −3.9; HRMS (ESI): Calculated C26H30Br2NaOSi2 [M+Na]+: 595.0100,Found: 595.0095.

(Z)-1-[(Dimethylphenylsilyloxy)-4-(2,4,6-triisopropylphenyl)but-3-en-1-yl]dimethylPhenylsilane(reaction time: 6 h, 80%). The compound was prepared from2-(2,4,6-triisopropylphenyl)furan.

colorless liquid; ¹H NMR (600 MHz, CDCl₃): δ 7.51-7.46 (m, 2H),7.46-7.41 (m, 2H), 7.40-7.31 (m, 4H), 7.29 (t, J=7.3 Hz, 2H), 7.05-6.90(m, 2H), 6.28 (d, J=11.6 Hz, 1H), 5.81-5.71 (m, 1H), 3.57 (dd, J=8.9,5.6 Hz, 1H), 3.12-2.98 (m, 2H), 2.95-2.85 (m, 1H), 2.17-2.09 (m, 1H),2.08-1.90 (m, 1H), 1.29 (d, J=6.8 Hz, 6H), 1.24-1.13 (m, 4H), 1.13-1.07(m, 8H), 0.23 (s, 3H), 0.21 (s, 3H), 0.19 (s, 6H); ¹³C NMR (150 MHz,CDCl₃): δ 147.4, 138.7, 137.5, 134.3, 133.8, 131.6, 131.1, 129.4, 129.1,128.2, 127.7, 127.7, 120.3, 120.3, 66.6, 34.4, 33.5, 30.2, 24.5, 24.3,23.2, −0.9, −1.1, −4.8, −5.0; ²⁹Si NMR (120 MHz, CDCl₃): δ 5.9, −4.5;HRMS (EI): Calculated for C35H50OSi2 [M]+: 542.3400, Found: 542.3396.

(Z)-1-[(Dimethylphenylsilyloxy)-4-(phenanthren-9-yl)but-3-en-1-yl]dimethylphenylsilane(reaction time: 3 h, 82%). The compound was prepared from2-(phenanthren-9-yl)furan.

colorless liquid; ¹H NMR (600 MHz, CDCl₃): δ 8.84-8.64 (m, 2H), 8.11 (d,8.0 Hz, 1H), 7.84 (d, J=7.7 Hz, 1H), 7.79-7.66 (m, 4H), 7.66-7.56 (m,2H), 7.52-7.38 (m, 6H), 7.34 (t, J=6.7 Hz, 1H), 7.26 (t, J=7.3 Hz, 2H),6.98 (d, J=11.8 Hz, 1H), 6.08 (dt, J=11.6, 7.3 Hz, 1H), 3.87 (dd, J=8.0,5.3 Hz, 1H), 2.70 (dt, J=15.5, 7.7 Hz, 1H), 2.58-2.49 (m, 1H), 0.4 (s,6H), 0.34 (s, 3H), 0.31 (s, 3H); ¹³C NMR (150 MHz, CDCl₃): δ 138.5,137.4, 134.3, 133.8, 132.8, 132.7, 131.7, 131.4, 130.5, 130.0, 129.5,129.1, 128.7, 128.3, 127.8, 127.7, 127.2, 126.7, 126.6, 126.5, 126.4,125.7, 123.0, 122.5, 67.0, 33.5, −0.8, −0.9, −4.7, −4.8; ²⁹Si NMR (120MHz, CDCl₃): δ 6.4, −4.3; HRMS (EI): Calculated for C34H36OSi2 [M]+:516.2305, Found: 516.2307.

(Z)-1,4-Bis[4-(dimethylphenylsilyl)-4-(dimethylphenylsilyloxy)but-1-en-1-yl]benzene(reaction time: 2 h, 72%). The compound was prepared from1,4-di(furan-2-yl) benzene using dimethylphenylsilane (4.0 equiv.).

colorless liquid; ¹H NMR (600 MHz, CDCl₃): δ 7.54 (d, J=6.4 Hz, 4H),7.49 (d, J=7.8 Hz, 4H), 7.41-7.35 (m, 8H), 7.33-7.28 (m, 4H), 6.36 (d,J=11.7 Hz, 2H), 5.84-5.53 (m, 2H), 3.86-3.71 (m, 2H), 2.76-2.61 (m, 2H),2.58-2.49 (m, 2H), 0.30 (s, 24H); ¹³C NMR (150 MHz, CDCl₃): δ 138.6,137.5, 135.8, 134.4, 133.8, 130.6, 129.8, 129.5, 129.2, 128.6, 127.8,67.0, 33.4, −0.7, −0.8, −4.8, −4.8; ²⁹Si NMR (120 MHz, CDCl₃): δ 6.4,−4.1; HRMS (EI): Calculated for C46H58O2Si4 [M]+: 754.3514, Found:754.3517.

(3Z,3′Z-{[(5-Bromo-1,3-phenylene)bis1-(dimethylphenylsilyloxy)but-3-ene-4,1-diyl]bis(dimethylphenylsilane)(reaction time: 8 h, 81%). The compound was prepared from2,2′-(5-bromo-1,3-phenylene)difuran.; B(C6F5)3(4.0 mol %) anddimethylphenylsilane (4.0 equiv.) were used.

colorless liquid; ¹H NMR (600 MHz, CDCl₃): δ 7.53 (d, J=7.2 Hz, 4H),7.48 (d, J=7.1 Hz, 4H), 7.42-7.29 (m, 14H), 6.95 (s, 1H), 6.26 (d,J=11.7 Hz, 2H), 5.76-5.55 (m, 2H), 3.76 (t, J=6.7 Hz, 2H), 2.71-2.53 (m,2H), 2.46-2.38 (m, 2H), 0.29 (s, 24H); ¹³C NMR (150 MHz, CDCl₃): δ139.1, 138.3, 137.1, 134.2, 133.6, 132.0, 129.5, 129.4, 129.1, 128.7,127.9, 127.7, 127.6, 121.8, 66.6, 33.0, −0.94, −0.97, −4.8, −4.9; ²⁹SiNMR (120 MHz, CDCl₃): δ 6.5, −4.1; HRMS (ESI): Calculated forC46H57BrNaO2Si4 [M+Na]+: 855.2517, Found: 855.2498.

(Z)-1,3,5-Tris[4-(dimethylphenylsilyl)-4-(dimethylphenylsilyloxy)but-1-en-1-yl]benzene(reaction time: 2.5 h, 87%). The compound was prepared from1,3,5-tri(furan-2-yl)benzene.; B(C6F5)3(6.0 mol %) anddimethylphenylsilane(6.0 equiv.) were used.

colorless liquid; ¹H NMR (600 MHz, CDCl₃): δ 7.58-7.52 (m, 6H),7.52-7.45 (m, 6H), 7.42-7.28 (m, 18H), 7.01 (s, 3H), 6.33 (d, J=12.5 Hz,3H), 5.74-5.61 (m, 3H), 3.78 (d, J=6.5 Hz, 3H), 2.72-2.61 (m, 3H),2.61-2.50 (m, 3H), 0.35-0.25 (m, 36H); ¹³C NMR (150 MHz, CDCl₃): δ138.4, 137.4, 137.1, 134.2, 133.6, 130.5, 129.9, 129.3, 129.1, 127.6,127.4, 66.8, 33.2, −0.8, −4.6, −4.9; ²⁹Si NMR (120 MHz, CDCl₃): δ 6.4,−4.2; HRMS (ESI): Calculated for C66H84NaO3Si6 [M+Na]+: 1115.4934,Found: 1115.4914.

Comparative Example 1

Comparative Example 1 was performed in the same way as in InventiveExample 1 above except that 2-methylfuran, PhMe₂SiH, and CD₂Cl₂ wereused during a reaction but a catalyst was not used, but an this case, noproduct was obtained on a ¹H NMR(1,1,2,2-tetrachloroethane (TCE))spectrum.

Comparative Example 2

Comparative Example 2 was performed in the same way as in InventiveExample 1 above except that 2-methylfuran, PhMe₂SiH, and CD₂Cl₂ wereused during a reaction like in Comparative Example 1 above but AlCl₃ wasused instead of a borane catalyst as a catalyst, but in this case, aproduct was obtained with a conversion yield of 10% and a yield of <1%(1% or less) on a ¹H NMR(1,1,2,2-tetrachloroethane (TCE)) spectrum.

Comparative Example 3

Comparative Example 3 was performed in the same way as in InventiveExample 1 above except that 2-methylfuran, PhMe₂SiH, and CD₂Cl₂ wereused during a reaction in Comparative Example 1 above but [Ir(COH)Cl]₂was used instead of a borane catalyst as a catalyst, but in this case, aproduct was obtained with a conversion yield of 10% and a yield of <1%on a ¹H NMR(1,1,2,2-tetrachloroethane (TCE)) spectrum.

Comparative Example 4

Comparative Example 4 was performed in the same way as in InventiveExample 1 above except that 2-methylfuran, PhMe₂SiH, and CD₂Cl₂ wereused during a reaction like in Comparative Example 1 above but[Rh(COD)Cl]₂ was used instead of a borane catalyst as a catalyst, but inthis case, a product was obtained with a conversion yield of 10% and ayield of <1% on a ¹H NMR(1,1,2,2-tetrachloroethane (TCE)) spectrum.

Comparative Example 5

Comparative Example 5 was performed in the same way as in InventiveExample 1 above except that 2-methylfuran, PhMe₂SiH, and CD₂Cl₂ wereused during a reaction like in Comparative Example 1 above butPt(0)-1,3-divinyl-1,1,3,3-tetramethyl-disiloxane was used instead of aborane catalyst as catalyst, but in this case, a product was obtainedwith a conversion yield of 12% and a yield of <1% on a ¹HNMR(1,1,2,2-tetrachloroethane (TCE)) spectrum.

Inventive Example 2 General Preparation of (Z)-α-silyloxyalkenylsilaneDerivative (Silyloxyalkenylsilanes)

CH₂Cl₂ (0.4-0.8 mL) and B(C₆F₅)₃ (0.01 to 0.02 mmol, 2.0 mol %) were putin a dried flask, a silane compound (PhMe₂SiH, 1.025-2.050 mmol) wasadded thereto and was well stirred and, then, a furan derivative (0.50to 1.0 mmol) was again added thereto and, then, was stirred at 23° C.for 3 to 12 hours. The reaction mixture was quenched with Et₃N (5.0 to10.0 mol %), was subjected to vacuum evaporation, and was isolated andpurified (to nucleic acid or hexane and ethyl acetate) via silica gelcolumn chromatography to obtain a target product (Z/E>99/1).

The following compound was prepared using the same method as the above.

(Z)-1-[(Dimethylphenylsilyloxy)but-2-en-1-yl]dimethylphenylsilane(reaction time: 12 h): The compound was prepared via a reaction betweenfuran (204 mg, 3.00 mmol) and dimethylphenylsilane (838 mg, 6.15 mmol)in the presence of B(C₆F₅)₃ (30.6 mg, 2.0 mol %) melted in CH₂Cl₂ (4.0mL) (746 mg, 73%).

colorless liquid; ¹H NMR (600 MHz, CDCl₃): δ 7.66-67.62 (m, 2H),7.60-7.52 (m, 2H), 7.45-7.35 (m, 6H), 5.56 (t, J=11.2 Hz, 1H), 5.43-5.32(m, 1H), 4.52 (d, J=9.9 Hz, 1H), 1.38 (d, J=8.4 Hz, 3H), 0.41 (s, 3H),0.36 (s, 9H); ¹³C NMR (150 MHz, CDCl₃): δ 138.8, 137.2, 134.5, 133.7,132.3, 129.4, 129.2, 127.7, 127.6, 121.8, 64.5, 13.5, −0.8, −1.0, −5.5,−5.7; ²⁹Si NMR (120 MHz, CDCl₃): δ 8.2, 4.8; HRMS (EI): Calculated forC20H28OSi2 [M]+: 340.1679, Found: 340.1676.

(Z)-[2-(4-tert-Butyl-phenyl)-1-(dimethylphenylsilyloxy)but-2-en-1-yl]dimethylphenylsilane(reaction time: 3 h, 84%). The compound was prepared from3-[4-(tert-butyl)phenyl]-furan.

colorless liquid; ¹H NMR (600 MHz, CDCl₃): δ 7.53 (d, J=7.2 Hz, 2H),7.48-7.40 (m, 3H), 7.39-3.34 (m, 3H), 7.30 (t, J=7.3 Hz, 3H), 7.22 (d,J=7.3 Hz, 3H), 5.57 (q, J=7.1 Hz, 1H), 4.79 (s, 1H), 1.88-1.53 (m, 3H),1.34 (s, 9H), 0.35 (s, 3H), 0.31 (s, 3H), 0.19 (s, 3H), 0.13 (s, 3H);¹³C NMR (150 MHz, CDCl₃): δ 149.3, 141.4, 140.6, 138.2, 137.8, 134.4,133.9, 129.5, 129.0, 127.9, 127.8, 127.5, 124.6, 124.2, 67.6, 34.5,31.5, 14.9, −1.0, −1.4, −4.4, −4.6; ²⁹Si NMR (120 MHz, CDCl₃): δ 8.4,−3.8; HRMS (EI): Calculated for C30H40OSi2 [M]+: 472.2618, Found:472.2616.

Inventive Example 3 General Preparation of γ-Silylated Ketone Derivative(γ-Silylated Ketone)

Preparation of 5-(Dimethylphenylsilyl)-3-methylpentan-2-one

1) CH₂Cl₂ (8.0 mL) and B(C₆F₅)₃ (0.102 g, 2.0 mol %) were put in a welldried flask at 0° C., dimethylphenylsilane (2.79 g, 20.5 mmol) was addedthereto and was stirred for 2 minutes, 2,3-dimethylfuran (0.96 g, 10.0mmol) was added again and, then, current temperature was increased, andthe resultant was stirred for 1 hour at 23° C. The reaction mixture wasquenched with Et₃N (50 mg, 0.5 mmol), was subjected to vacuumevaporation and, then, was used in the following reaction.

2) THF (5 mL) was added to the reaction mixture in the above step,tetrabutylammonium fluoride (TBAF) (1 M in THF, 20 m1, 20.0 mmol) wasslowly added thereto at 0° C., current temperature was increased again,and the resultant was stirred at 23° C. for 2 hours. Water (20 mL) wasadded to the reaction mixture and the resultant was subject toextraction with ethyl acetate (15 mL×3). The collected organic layerswere dried with anhydrous Na₂SO₄, were subjected to vacuum evaporation,and were isolated and purified via silica gel column chromatography(ethyl acetate/hexane 1/9) to obtain a target compound (1.71 g, 73% fortwo steps).

colorless liquid; ¹H NMR (600 MHz,CDCl₃): δ 7.54-7.47 (m, 2H), 7.40-7.30(m, 3H), 2.53-2.40 (m, 1H), 2.07 (s, 3H), 1.73-1.58 (m, 1H), 1.45-1.32(m, 1H), 1.06 (d, J=6.9 Hz, 3H), 0.78-0.62 (m, 2H), 0.28 (s, 6H); ¹³CNMR (150 MHz, CDCl₃): δ 212.6, 138.8, 133.5, 128.9, 127.8, 49.8, 28.1,27.2, 15.7, 13.0, −3.19, −3.27; ²⁹Si NMR (120 MHz, CDCl₃): δ −2.8; HRMS(ESI): Calculated for C14H22NaOSi [M+Na]+: 257.1338, Found: 257.1330.

Inventive Example 4 General Preparation of (Z)-HomoallylsilaneDerivative ((Z)-Homoallylsilane)

CH₂Cl₂ (0.8 mL) and B(C₆F₅)₃ (0.02 mmol, 2.0 mol %) were put in a welldried flask, diphenylsilane (2.0 mmol) was added thereto and was wellstirred, furan derivative (1.0 mmol) was added again, currenttemperature was increased and, then, the resultant was stirred at 23° C.for 1 hour. The reaction mixture was quenched with Et₃N (5 mmol %), wassubjected to vacuum evaporation and, then, was isolated and purified (tohexane) via silica gel column chromatography to obtain a target compound(Z/E>99/1).

The following compound was prepared using the same method as the above.

(Z)-1-(Hex-4-en-2-yl)-1,1,3,3-tetraphenyldisiloxane (reaction time: 1 h,81%). The compound was prepared from 2,5-dimethylfuran.

colorless liquid; ¹H NMR (600 MHz,CDCl₃): δ7.71-7.56 (m, 8H), 7.50-7.30(m, 12H), 5.73 (s, 1H), 5.55-5.43 (m, 1H), 5.42-5.32 (m, 1H), 2.34 (d,J=11.2 Hz, 1H), 2.00 (d, J=10.1 Hz, 1H), 1.48(d, J=5.8 Hz, 3H),1.45-1.33 (m, 1H), 1.05 (d, J=7.2 Hz, 3H); ¹³C NMR (150 MHz, CDCl₃): δ135.6, 135.4, 134.8, 134.5, 130.5, 130.3, 129.8, 128.05, 127.9, 124.5,28.2, 20.2, 13.5, 12.9; ²⁹Si NMR (120 MHz, CDCl³): δ −8.4, −20.6; HRMS(EI): Calculated for C30H32OSi2 [M]+: 464.1992, Found: 464.1994.

Inventive Example 5 General Preparation of Ortho-(β-Silylethyl)-PhenolDerivative (Ortho-(β-Silylethyl)-Phenols)

CH₂Cl₂ (0.4 mL) and B(C₆F₅)₃ (0.025 mmol, 5.0 mol %) were put in a welldried flask, dimethylphenylsilane (1.05 to 1.5 mmol) was added theretoand was well stirred and, then, a benzofuran derivative (0.5 mmol) wasadded again, current temperature was increased, and the resultant wasstirred at 23° C. for 3 to 7 hours. K₂CO₃ (138 mg, 1.00 mmol) melted inmethanol (2 mL) was added to the reaction mixture and was stirred at 23°C. for 5 to 7 hours. The resultant was filtered with celite to remove asolid, was subjected to vacuum evaporation and, then, was isolated andpurified (to hexane/ethyl acetate) via silica gel column chromatographyto prepare a target compound.

The following compound was prepared using the same method as the above.

2-[2-(Dimethylphenylsilyl)ethyl]phenol (reaction time: 5 h, 90%).

colorless liquid; ¹H NMR (600 MHz, CDCl₃): δ 7.64-7.52 (m, 2H),7.45-7.31 (m, 3H), 7.14 (d, J=7.3 Hz, 1H), 7.07 (t, J=8.3 Hz, 1H), 6.88(t, J=7.7 Hz, 1H), 6.73 (d, J=7.9 Hz, 1H), 4.69 (s, 1H), 2.97-2.41 (m,2H), 1.29-0.96 (m, 2H), 0.33 (s, 6H); ¹³C NMR (150 MHz, CDCl₃): δ 153.3,139.2, 133.7, 130.9, 129.4, 129.1, 127.9, 127.0, 120.9, 115.3, 24.2,15.9, −2.9; ²⁹Si NMR (120 MHz, CDCl₃): δ −2.7; HRMS (EI): Calculated forC16H20OSi [M]+: 256.1283, Found: 256.1286.

2-[2-(Dimethylphenylsilyl)propyl]phenol (reaction time: 3 h, 88%). Thecompound was prepared from 2-methylbenzofuran.

colorless liquid; ¹H NMR (600 MHz,CDCl₃): δ 7.77-77.56 (m, 2H),7.51-7.32 (m, 3H), 7.16-7.02 (m, 2H), 6.87 (t, J=6.0 Hz, 1H), 6.75 (d,J=6.0 Hz, 1H), 4.60 (s, 1H), 2.88 (dd, J=12.0, 6.0 Hz, 1H), 2.19 (d,J=12.0 Hz, 1H), 1.56-1.21 (m, 1H), 0.94 (d, J=7.3 Hz, 3H), 0.37 (s, 6H);¹³C NMR (150 MHz, CDCl₃): δ 153.7, 138.4, 134.1, 130.9, 129.1, 127.9,127.1, 120.5, 115.4, 32.0, 20.3, 13.9, −4.7, −5.2; ²⁹Si NMR (120 MHz,CDCl₃): δ 0.55; HRMS (EI): Calculated for C17H22OSi [M]+: 270.1440,Found: 270.1440.

2-{2-(Dimethylphenylsilyl)-2-[4-(triisopropylsilyloxy)phenyl]ethylphenol (reaction time: 7 h, 70%). The compound was prepared from2-(naphthalen-1-yl)benzofuran.

colorless liquid; ¹H NMR (600 MHz,CDCl₃): δ 7.53-7.44 (m, 2H), 7.41-7.31(m, 3H), 6.98-6.89 (m, 1H), 6.82-6.75 (m, 3H), 6.74-4 6.68 (m, 2H),6.66-6.56 (m, 2H), 4.55-4.27 (m, 1H), 3.07 (dd, J=14.7, 3.2 Hz, 1H),2.96-2.85 (m, 1H), 2.49 (dd, J=11.7, 3.2 Hz, 1H), 1.27-1.18 (m, 3H),1.14-0.89 (m, 18H), 0.34 (s, 3H), 0.24 (s, 3H); ¹³C NMR (150 MHz,CDCl₃): δ 153.5, 137.7, 135.1, 134.3, 130.5, 129.4, 129.3, 129.1, 128.5,127.8, 127.0, 120.6, 120.1, 115.6, 36.5, 31.0, 18.0, 12.7, −3.8, −4.9;²⁹Si NMR (120 MHz, CDCl₃): δ 15.2, −1.8; HRMS (EI): Calculated forC31H44O2Si2 [M]+: 504.2880, Found: 504.2879.

2-[2-(Dimethylphenylsilyl)-2-phenylethyl]phenol (reaction time: 4 h,79%). The compound was prepared from 2-phenylbenzofuran.

colorless liquid; ¹H NMR (600 MHz,CDCl₃): δ 7.57-7.49 (m, 2H), 7.47-7.32(m, 3H), 7.19 (t, J=6.7 Hz, 2H), 7.09 (t, J=7.3 Hz,1H), 7.04-7.90 (m,3H), 6.85 (d, J=7.4 Hz, 1H), 6.69 (t, J=6.9 Hz, 1H), 6.62 (d, J=7.9 Hz,1H), 4.47 (s, 1H), 3.11 (d, J=14.4 Hz, 1H), 3.03 (t, J=13.0 Hz, 1H),2.66 (d, J=10.6 Hz, 1H), 0.37 (s, 3H), 0.26 (s, 3H); ¹³C NMR (150 MHz,CDCl₃): δ 153.5, 142.7, 137.5, 134.3, 130.4, 129.3, 128.3, 128.3, 128.2,127.9, 127.1, 125.0, 120.6, 115.5, 37.2, 30.5, −3.7, −5.1; ²⁹Si NMR (120MHz, CDCl₃): δ −1.3; HRMS (EI): Calculated for C22H24OSi [M]+: 332.1596,Found: 332.159.

Inventive Example 6 Example 1 of Application of the Silane DerivativeAccording to the Present Invention

Preparation of (Z)-1-(Dimethylphenylsilyl)pent-3-en-1-ol (reaction time:4 h, 90%). The compound was prepared from K2CO3 (2.76 g, 20 mmol), MeOH(40 mL), and Z-2 (3.54 g, 10.0 mmol).

colorless liquid; ¹H NMR (600 MHz,CDCl₃): δ 7.65-7.55 (m, 2H), 7.43-7.34(m, 3H), 5.75-5.57 (m, 1H), 5.49-5.31 (m, 1H), 3.49 (dd, J=12, 6.0 Hz,1H), 2.49-2.33 (m, 1H), 2.26-2.07 (d, J=14.4 Hz, 1H), 1.61 (d, J=6.7 Hz,3H), 1.53-1.33 (m, S1 31H), 0.39 (s, 3H), 0.37 (s, 3H); ¹³C NMR (150MHz, CDCl₃): δ 136.9, 134.2, 129.4, 127.9, 127.6, 127.5, 64.6, 31.1,13.1, −5.3, −5.3; ²⁹Si NMR (120 MHz, CDCl₃): δ −3.8; HRMS (EI):Calculated for C13H20OSi [M]+: 220.1283, Found: 220.1279.

Preparation of(Z)-1-[(Dimethylphenylsilyl)(pent-3-en-1-yl)]-3,5-dinitrobenzoate

(Z-2″, 83%). Z-2′ (1.00 g, 4.54 mmol) and CH₂Cl₂ (40 mL) were put in awell dried flask, triethylamine (Et₃N) (2.3 g, 22.7 mmol),dimethylaminopyridine (DMAP) (0.910 mmol, 111 mg, 20.0 mol %), and3,5-dinitrobenzoylchloride (1.36 g, 5.9 mmol) were slowly added theretoat 0° C., and were stirred at 23° C. for 16 hours. The reaction mixturewas diluted with CH₂Cl₂, was quenched with water (5 mL), was extractedwith CH₂Cl₂ and, then, was washed with salt water. An organic layer wasdried with Mg₂SO₄, was subjected to vacuum evaporation and, then, wasisolated and purified (to ethyl acetate/hexane 1/10) via silica gelcolumn chromatography to obtain a target compound Z-2″ (1.553 g, 83%).The resultant was re-crystallized with CH₂Cl₂ and n-pentane to obtain acompound of yellow crystals.

m.p. 79-81° C; ¹H NMR (600 MHz,CDCl₃): δ 9.19 (s, 1H), 9.02 (s, 2H),7.57 (s, 2H), 7.38 (s, 3H), 5.53-5.44 (m, 1H), 5.37-5.32 (m, 1H),5.31-5.26 (m, 1H), 2.71-2.55 (m, 1H), 2.46-2.28 (m, 1H), 1.54 (d, J=6.6Hz, 3H), 0.45 (s, 6H); ¹³C NMR (100 MHz, CDCl₃): δ 162.7, 148.8, 135.0,134.5, 134.1, 130.0, 129.3, 128.2, 126.9, 126.3, 122.2, 71.6, 28.8,13.0, −4.7, −4.8; ²⁹Si NMR (120 MHz, CDCl₃): δ −2.6; HRMS (EI):Calculated for C20H22N2O6Si [M]+: 414.1247, Found: 414.1244.

Inventive Example 7 Example 2 of Application of Silane DerivativeAccording to the Present Invention

In a light-blocked container, (dimethylphenylsilyl)pent-3-en-1-ol (Z-2′,0.22 g, 1.0 mmol) was melted in benzene (14 mL) and Pb(OAc)₄ (0.488 g,1.1 mmol) was added at 0° C. and under nitrogen gas. The resultant wasfiltered after a reaction at 23° C. for 2 hours to remove a solid, wassubjected to vacuum evaporation, and was isolated and purified (tohexane/ethylacetate 9/1) via silica gel column chromatography to obtaina colorless liquid compound (Z-55).

colorless liquid (0.209 g, 75%); ¹H NMR (600 MHz,CDCl₃): δ 7.59 (d,J=1.6 Hz, 1H), 7.58 (d, J=1.7 Hz, 1H), 7.40-7.34 (m, 3H), 6.00 (t, J=5.3Hz, 1H), 5.64-5.54 (m, 1H), 5.40-5.30 (m, 1H), 2.48-2.34 (m, 2H), 1.91(s, 3H), 1.58 (d, J=6.9 Hz, 3H), 0.44 (s, 3H), 0.43 (s, 3H); ¹³C NMR(150 MHz, CDCl₃): δ 169.9, 137.0, 133.5, 129.7, 127.7, 127.5, 123.2,92.1, 34.4, 21.1, 12.9, −1.4; ²⁹Si NMR (120 MHz, CDCl₃): δ 8.8; IR(cm¹): 2958, 1737, 1590, 1427, 1370, 1238, 1117, 1007, 935, 823, 699;HRMS (ESI): Calculated for C15H22NaO3Si [M+Na]+: 301.1236, Found:301.1230

Inventive Example 8 Example 3 of Application of Silane DerivativeAccording to the Present Invention

Preparation of(Z)-2-[1-(Dimethylphenylsilyl)pent-3-en-1-yl]isoindoline-1,3-dione(Z-56).

(Z)-1-(dimethylphenylsilyl)pent-3-en-1-ol (Z-2′, 0.22 g, 1.0 mmol),triphenylphosphine (TPP, 0.34 g, 1.3 mmol), and phthalimide (0.191 g,1.3 mmol) were melted in THF (2.0 mL), diethyl azodicarboxylate (DEAD,226 g, 1.3 mmol) was slowly added thereto at 0° C. under nitrogen gas,and was stirred at 23° C. for 20 hours. The reaction mixture wassubjected to vacuum evaporation and was isolated and purified (tohexane/ethyl acetate 9/1) via silica gel column chromatography to obtaina colorless and viscous liquid Z-56.

colorless viscous oil (0.265 g, 76%). ¹H NMR (600 MHz, CDCl₃): δ7.79-7.72 (m, 2H), 7.68-7.61 (m, 2H), 7.60-7.53 (m, 2H), 7.35-7.29 (m,3H), 5.49-5.34 (m, 1H), 5.34-5.18 (m, 1H), 4.03 (dd, J=11.6, 4.5 Hz,1H), 2.99-2.83 (m, 1H), 2.41-2.25 (m, 1H), 1.6 (d, J=6.7 Hz, 3H), 0.59(s, 3H), 0.45 (s, 3H); ¹³C NMR (100 MHz, CDCl₃): δ 168.9, 136.8, 133.8,133.6, 131.9, 129.3, 127.8, 127.5, 126.6, 122.8, 41.1, 26.0, 12.6, −3.3,−3.8; ²⁹Si NMR (80 MHz, CDCl₃):δ −0.3; IR (cm¹): 2954, 1770, 1705, 1466,1427, 1385, 1249, 1172, 1078, 985, 882, 717; HRMS (ESI): Calculated forC21H23NNaO2Si [M+Na]+: 372.1396, Found: 372.1383

Inventive Example 9 Example 4 of Application of Silane DerivativeAccording to the Present Invention

Preparation of2-[(4-Bromophenyl)-6-(dimethylphenylsilyl)]-3-methyltetrahydro-2H-pyran-4-ol

(Z)-1-(dimethylphenylsilyl)pent-3-en-1-ol (Z-2′, 0.22 g, 1.0 mmol) and4-bromobenzaldehyde (0.221 g, 1.2 mmol) were melted in CH₂Cl₂ (5 mL),trifluoroacetic acid (0.285 g, 2.25 mmol) was slowly added thereto at−20° C. under nitrogen gas and, then, a reaction was performed at thesame temperature for 3 hours. The resultant was quenched with 5 mL of asaturated sodium hydrogen carbonate (NaHCO₃) solution and, then,triethylamine was added thereto to satisfy pH>7. Organic layerscollected via extraction with CH₂Cl₂ (3×5 mL) were dried with anhydrousNa₂SO₄ and were subjected to vacuum evaporation. MeOH (6 mL) was addedthereto, K₂CO₃ (0.276 g, 2.0 mmol) was added at 0° C., and a reactionwas performed for 2 hours. When the reaction was completed, theresultant was filtered with celite, and was subjected to vacuumevaporation, and was isolated and purified (to hexane/ethyl acetate 7/3)via silica gel column chromatography to obtain a colorless liquidcompound 58 (0.230 g, 57% for two steps).

colorless liquid with single diastereomer. ¹H NMR (600 MHz,CDCl₃): δ7.69-7.58 (m, 2H), 7.47 (d, J=4.9 Hz, 2H), 7.42-7.33 (m, 3H), 7.17 (d,J=5.1 Hz, 2H), 4.41 (d, J=3.4 Hz, 1H), 4.07-4.00 (m, 1H), 3.46 (d,J=13.2 Hz, 1H), 2.21-2.12 (m, 1H), 1.80-1.71 (m, 1H), 1.67 (q, J=13.0Hz, 1H), 1.60-1.52 (m, 1H), 0.57 (d, J=3.5 Hz, 3H), 0.42 (s, 6H); ¹³CNMR (150 MHz, CDCl₃): δ 140.8, 136.4, 134.1, 131.1, 129.3, 127.8, 127.1,120.2, 81.8, 72.2, 70.0, 40.7, 30.0, 4.9, −5.4, −5.6; ²⁹Si NMR (120 MHz,CDCl₃): δ −4.7; IR (cm¹): 3369, 2968, 1707, 1589, 1488, 1361, 1247,1114, 1009, 817, 699; HRMS (ESI): Calculated for C20H25BrNaO2Si [M+Na]+:427.0705, Found: 427.0688.

Preparation of[(4-Bromophenyl)-6-(dimethylphenylsilyl)]-3-methyltetrahydro-2H-pyran-4-yl-3,5-dinitrobenzoate(Compound 58′)

Compound 58 (40.4 mg, 0.1 mmol) prepared as described above was meltedin CH₂Cl₂ (2 mL), triethylamine (51 mg, 0.3 mmol,) and4-dimethylaminopyridine (DMAP, 0.1 mg, 0.001 mmol, 1 mol %) were addedthereto and, then, 3,5-dinitrobenzoyl chloride (28 mg, 0.12 mmol) wasslowly added again at 0° C. The reaction mixture was stirred at 23° C.for 12 hours. Water (3 mL) was added to the reaction mixture and wassubjected to extraction with CH₂Cl₂ (3 mL×3). The collected organiclayers were dried with anhydrous Na₂SO₄, were subjected to vacuumevaporation, and were isolated and purified (to hexane/ethyl acetate8/2) via silica gel chromatography to obtain a single stereoisomercompound 58′ (56 mg, 94%). The resultant was re-crystallized with ethylacetate and hexane to obtain a yellow color solid.

Yellow color solid; m.p. 145-147° C.; ¹H NMR (600 MHz,CDCl₃): δ 9.21 (t,J=2.1 Hz, 1H), 9.11 (d, J=2.1 Hz, 2H), 7.67-7.55 (m, 2H), 7.47 (d, J=8.5Hz, 2H), 7.43-7.33 (m, 3H), 7.18 (d, J=8.1 Hz, 2H), 5.56-5.46 (m, 1H),4.59 (d, J=1.4 Hz, 1H), 3.60 (dd, J=13.3, 2.4 Hz, 1H), 2.50-2.44 (m,1H), 1.99 (td, J=13.0, 11.6 Hz, 1H), 1.79-1.71 (m, 1H), 0.70 (d, J=6.9Hz, 3H), 0.45 (s, 3H), 0.44 (s, 3H); ¹³C NMR (150 MHz, CDCl₃): δ 161.7,148.6, 139.7, 135.8, 134.1, 134.06, 131.2, 129.5, 129.3, 127.9, 127.0,122.4, 120.6, 81.6, 77.6, 70.0, 37.9, 26.7, 6.0, −5.4, −5.6; ²⁹Si NMR(120 MHz, CDCl₃): δ −4.2; IR (cm¹): 3099, 1728, 1628, 1546, 1487, 1343,1277, 1168, 1047, 906, 783; HRMS (ESI): Calculated for C27H27BrN2NaO7Si[M+Na]+: 621.0669, Found: 621.0684.

The method of preparing a silane derivative via a reaction between afuran derivative and a silane compound in the presence of a boranecatalyst according to the present invention may not use transition metalas a catalyst and, thus, may synthesize a silane derivative with a highyield via high stereoselectivity even under an eco-friendly and mildcondition, in detail, using low temperature and short reaction time.

Accordingly, the method of preparing a silane derivative according tothe present invention may be easily and commercially applied to bemass-produced.

In addition, the silane derivative prepared using the method ofpreparing a silane derivative according to the present invention may beused as an intermediate of various compounds as described in InventiveExamples 6 to 9 according to the present invention and, thus, may beused as an intermediate or raw material in various ways such assynthesis of medicines and natural products.

II. Preparation of Anti-Cyclopropyl Silane Compound from Furan CompoundInventive Example 10 Preparation ofanti-(2-Ethylcyclopropyl)dimethylphenylsilane (Anti-33)

B(C₆F₅)₃ (0.025 mmol, 5.0 mol %) was dissolved in CH₂Cl₂ (0.2 mL),dimethylphenylsilane (2.0 mmol) was added thereto and, then, theresultant was stirred. 2-methylfuran (0.50 mmol) was added at 0° C. andthe reaction mixture was stirred at 23° C. for 6 hours. Et₃N (5 eq basedon B(C₆F₅)₃) was added to complete a reaction and, then, was subjectedto vacuum evaporation. The evaporated crude product was purified viasilica gel flash column chromatography (eluant: hexane or mixture ofhexane and ethyl acetate) to obtainanti-(2-Ethylcyclopropyl)dimethylphenylsilane (anti-33) (yield of 83%,dr.>99/1).

Colorless liquid; ¹H NMR (600 MHz, CDCl₃): δ 7.82-7.76 (m, 2H),7.56-7.52 (m, 3H), 1.69-1.59 (m, 1H), 1.48-1.38 (m, 1H), 1.19 (t, J=7.3Hz, 3H), 0.92-0.83 (m, 1H), 0.69-0.59 (m, 2H), 0.43 (s, 3H), 0.41 (s,3H), −0.17-−0.30 (m, 1H); ¹³C NMR (150 MHz, CDCl₃): δ 139.6, 133.9,128.9, 127.8, 29.1, 17.8, 14.13, 9.1, 3.4, −3.4, −3.7; ²⁹Si NMR (120MHz, CDCl₃): δ −2.9; HRMS (EI): Calculated for C₁₃H₂₀Si [M]⁺: 204.1334,Found: 204.1333.

Inventive Example 11 Preparation ofanti-(2-Ethylcyclopropyl)diphenylsilane (Anti-36)

Anti-(2-Ethylcyclopropyl)diphenylsilane (anti-36) (yield of 81%,dr.>99/1) was obtained via a reaction between 2-methylfuran (164 mg, 2.0mmol) and diphenylsilane (1.11 g, 6.0 mmol) for 4 hours using B(C₆F₅)₃(51 mg, 5.0 mol %) dissolved in CH₂Cl₂ (1.0 mL) in the same method asInventive Example 10.

colorless liquid; ¹H NMR (600 MHz, CDCl₃): δ 7.69 (d, J=6.9 Hz, 4H),7.51-7.39 (m, 6H), 4.79 (d, J=3.8 Hz, 1H), 1.50-1.27 (m, 2H), 1.07 (t,J=7.3 Hz, 3H), 0.91-0.80 (m, 1H), 0.71-0.49 (m, 2H), −0.03-−0.18 (m,1H); ¹³C NMR (150 MHz, CDCl₃): δ 135.5, 134.6, 129.7, 127.9, 28.8, 18.6,13.9, 9.7, 0.12; ²⁹Si NMR (120 MHz, CDCl₃): δ −10.7; HRMS (EI):Calculated for C₁₇H₂₀Si [M]⁺: 252.1334, Found 252.1336.

Inventive Example 12 Preparation ofanti-(2-Propylcyclopropyl)dimethylphenylsilane (Anti-37)

Anti-(2-Propylcyclopropyl)dimethylphenylsilane (anti-37) (yield of 77%,dr.>99/1) was obtained via a reaction for 5 hours using the same methodas Inventive Example 10 above except that 2-ethylfuran was used insteadof 2-methylfuran.

colorless liquid; ¹H NMR (600 MHz, CDCl₃): δ 7.72-7.62 (m, 2H),7.49-7.40 (m, 3H), 1.57-1.41 (m, 3H), 1.35-1.20 (m, 1H), 1.07-0.94 (m,3H), 0.84-0.73 (m, 1H), 0.58-0.43 (m, 2H), 0.30 (s, 3H), 0.28 (s, 3H),−0.30-−0.41 (m, 1H); ¹³C NMR (150 MHz, CDCl₃): δ 139.7, 133.9, 128.9,127.8, 38.3, 23.1, 15.7, 14.2, 9.2, 3.4, −3.4, −3.7; ²⁹Si NMR (120 MHz,CDCl₃): δ −2.9; HRMS (EI): Calculated for C₁₄H₂₂Si [M]⁺: 218.1491, Found218.1495.

Inventive Example 13 Preparation ofanti-(2-Butylcyclopropyl)dimethylphenylsilane (Anti-38)

Anti-(2-Butylcyclopropyl)dimethylphenylsilane (anti-38) (yield of 66%,dr.>99/1) was obtained via a reaction for 5 hours using the same methodas Inventive Example 10 except that 2-propylfuran was used instead of2-methylfuran.

colorless liquid; ¹H NMR (600 MHz, CDCl₃): δ 7.67-7.56 (m, 2H),7.48-7.29 (m, 3H), 1.47-1.31 (m, 5H), 1.28-1.17 (m, 1H), 0.97-0.90 (m,3H), 0.79-0.59 (m, 1H), 0.52-0.38 (m, 2H), 0.25 (s, 3H), 0.22 (s, 3H),−0.33-0.49 (m, 1H); ¹³C NMR (150 MHz, CDCl₃): δ 139.7, 133.9, 128.9,127.8, 35.8, 32.3, 22.7, 15.9, 14.3, 9.3, 3.5, −3.5, −3.7; ²⁹Si NMR (120MHz, CDCl₃): δ −2.9; HRMS (EI): Calculated for C₁₅H₂₄Si [M]+: 232.1647,Found: 232.1646.

Inventive Example 14 Preparation ofanti-(2-Hexcyclopropyl)dimethylphenylsilane (Anti-39)

Anti-(2-Hexcyclopropyl)dimethylphenylsilane (anti-39) (yield of 83%,dr.>99/1) was obtained via a reaction using the same method as InventiveExample 10 above except that 2-pentylfuran was used instead of2-methylfuran.

colorless liquid; ¹H NMR (600 MHz, CDCl₃): δ 7.73-7.53 (m, 2H),7.36-7.01 (m, 3H), 1.42-1.04 (m, 10H), 0.91-0.77 (m, 3H), 0.70-0.58 (m,1H), 0.49-0.29 (m, 2H), 0.16 (s, 3H), 0.14 (s, 3H), −0.45-−0.55 (m, 1H);¹³C NMR (150 MHz, CDCl₃): δ 139.3, 133.5, 128.5, 127.4, 76.8, 35.7,31.8, 29.6, 29.0, 22.5, 15.6, 13.9, 8.9, 3.1, −3.8, −4.1; ²⁹Si NMR (120MHz, CDCl₃): δ −2.9; HRMS (EI): Calculated for C₁₇H₂₃Si [M]⁺: 260.1960,Found: 260.1962.

Inventive Example 15 Preparation ofanti-2-{2-[(1,1′-Biphenyl-4-yl)ethyl]cyclopropyl}dimethylphenylsilane(Anti-40)

B(C₆F₅)₃ (0.025 mmol, 5.0 mol %) was dissolved in CH₂Cl₂ (0.2 mL),dimethylphenylsilane (2.0 mmol) was added thereto, and the resultant wasstirred. 2-[(1,1′-biphenyl)-4-ylmethyl]furan (1ac, 0.50 mmol) was addedat 0° C. and the reaction mixture was stirred at 23° C. for 6 hours.Et₃N (5 eq based on B(C₆F₅)₃) was added thereto to complete a reaction.

Then, the resultant was subjected to vacuum evaporation, was dilutedwith THF (0.5 ml) and, then, was cooled to 0° C., and tetrabutylammoniumfluoride (TBAF) (1 M in THF, 3.0 mL) was slowly applied thereto and,then, was stirred at 55° C. After 12 hours elapsed, the resultant wascooled to 23° C., water (5 mL) was added thereto to complete a reactionand, then, the resultant was subjected to extraction with ethyl acetate(5 mL×3). The obtained organic layer was subjected to vacuumevaporation. The evaporated crude product was purified via silica gelflash column chromatography (eluant: hexane or mixture of hexane andethyl acetate) to obtainanti-2-{2-[(1,1′-Biphenyl-4-yl)ethyl]cyclopropyl}dimethylphenylsilane(anti-40) (yield of 74%, dr.>99/1).

colorless liquid; ¹H NMR (600 MHz, CDCl₃): δ 7.71 (t, J=7.0 Hz, 4H),7.63 (d, J=8.0 Hz, 2H), 7.54 (t, J=7.6 Hz, 2H), 7.50-7.46 (m, 3H), 7.44(t, J=6.9 Hz, 1H), 7.35 (d, J=7.9 Hz, 2H), 2.92-2.81 (m, 2H), 1.93-1.84(m, 1H), 1.73-1.62 (m, 1H), 0.94-0.82 (m, 1H), 0.67-0.52 (m, 2H), 0.35(s, 3H), 0.33 (s, 3H), −0.19-−0.28 (m, 1H); ¹³C NMR (150 MHz, CDCl₃): δ141.8, 141.3, 139.4, 138.7, 133.9, 128.9, 128.9, 128.8, 127.8, 127.1,38.0, 35.9, 15.9, 9.3, 3.9, −3.5, −3.6; ²⁹Si NMR (120 MHz, CDCl₃): δ−2.9; HRMS (ESI): Calculated for C₂₅H₂₈NaSi [M+Na]⁺: 379.1858, Found:379.1852.

Inventive Example 16 Preparation ofanti-{2-[4-(Trifluoromethyl)benzyl]cyclopropyl}dimethylphenylsilane(Anti-41)

Anti-{2-[4-(Trifluoromethyl)benzyl]cyclopropyl}dimethylphenylsilane(anti-41) (yield of 80%, dr.>99/1) was obtained via a reaction using thesame method as Inventive Example 15 except that2-[4-(trifluoromethyl)phenyl]-furan (1e) was used instead of2-[(1,1′-biphenyl)-4-ylmethyl]furan (1ac).

colorless liquid; ¹H NMR (600 MHz, CDCl₃): δ 7.54 (d, J=7.8 Hz, 2H),7.48 (d, J=6.9 Hz, 2H), 7.39 (d, J=9.9 Hz, 1H), 7.34 (t, J=7.1 Hz, 4H),2.82 (dd, J=14.7, 6.3 Hz, 1H), 2.59 (dd, J=14.6, 7.1 Hz, 1H), 1.04-0.94(m, 1H), 0.68-0.56 (m, 2H), 0.22 (s, 3H), 0.17 (s, 3H), −0.13-−0.31 (m,1H); ¹³C NMR (150 MHz, CDCl₃): δ 146.2, 139.0, 133.8, 129.1, 128.8,127.8, 126.2, 125.3 (q, J=3.7 Hz), 124. (q, J=273 Hz), 41.5, 16.8, 9.3,3.9, −3.6, −3.9; ²⁹Si NMR (120 MHz, CDCl₃): δ −2.9; ¹⁹F NMR (CDCl₃, 375MHz): −62.3; HRMS (EI): Calculated for (C₁₉H₂₁F₃Si [M]⁺: 334.1365,Found: 334.1367.

Inventive Example 17 Preparation ofanti-[(4-Fluorobenzyl)cyclopropyl]dimethylphenylsilane (Anti-42)

Anti-[(4-Fluorobenzyl)cyclopropyl]dimethylphenylsilane (anti-42) (yieldof 64%, dr.>99/1) was obtained using the same method as InventiveExample 15 except that 2-(4-fluorophenyl) furan (1f) was used instead of2-[(1,1′-biphenyl)-4-ylmethyl]furan (1ac).

Colorless liquid; ¹H NMR (600 MHz, CDCl₃): δ 7.44 (d, J=6.0 Hz, 2H),7.39-7.30 (m, 3H), 7.22-7.13 (m, 2H), 7.02-6.92 (m, 2H), 2.70 (dd,J=14.3, 6.7 Hz, 1H), 2.50 (dd, J=14.4, 7.0 Hz, 1H), 0.98-0.91 (m, 1H),0.64-0.52 (m, 2H), 0.17 (s, 3H), 0.14 (s, 3H), −0.12-−0.32 (m, 1H); ¹³CNMR (150 MHz, CDCl₃): δ 161.5 (d, J=243.2 Hz), 139.18, 137.79-137.62 (dJ=3.0 Hz), 133.86, 129.01, 129.82 (d, J=7.8 Hz), 127.81, 115.05 (d,J=21.0 Hz), 40.87, 17.15, 9.26, 3.73, −3.64, −3.76; ²⁹Si NMR (120 MHz,CDCl₃): δ −2.9; ¹⁹F NMR (CDCl₃, 375 MHz): δ −117.9; HRMS (EI):Calculated for C₁₃H₂₁FSi [M]⁺: 284.1397, Found: 284.1399.

Inventive Example 18 Preparation ofanti-2-[(4-Chlorobenzyl)cyclopropyl]dimethylphenylsilane (Anti-43)

Anti-2-[(4-Chlorobenzyl)cyclopropyl]dimethylphenylsilane (anti-43)(yield of 80%, dr.>99/1) was obtained via a reaction using the samemethod as Inventive Example 15 except that 2-(4-chlorophenyl)furan (1g)was used instead of 2-[(1,1′-biphenyl)-4-ylmethyl]furan (1ac).

Colorless liquid; ¹H NMR (600 MHz, CDCl₃): δ 7.48 (d, J=7.5 Hz, 2H),7.41-7.30 (m, 3H), 7.24 (d, J=7.5 Hz, 2H), 7.15 (d, J=7.9 Hz, 2H), 2.72(dd, J=14.5, 6.3 Hz, 1H), 2.51 (dd, J=14.5, 7.0 Hz, 1H), 1.00-0.91 (m,1H), 0.66-0.53 (m, 2H), 0.20 (s, 3H), 0.16 (s, 3H), −0.17-−0.29 (m, 1H);¹³C NMR (150 MHz, CDCl₃): δ 140.5, 139.1, 133.8, 131.7, 129.9, 129.0,128.4, 127.8, 41.0, 16.9, 9.3, 3.8, −3.6, −3.8; ²⁹Si NMR (120 MHz,CDCl₃): δ −2.9; HRMS (EI): Calculated for C₁₈H₂₁ClSi [M]⁺: 300.1101,Found: 300.1097.

Inventive Example 19 Preparation ofanti-2-[(4-Bromobenzyl)cyclopropyl]dimethylphenylsilane (Anti-44)

Anti-2-[(4-Bromobenzyl)cyclopropyl]dimethylphenylsilane (anti-44) (yieldof 71%, dr.>99/1) was obtained via a reaction using the same method asInventive Example 15 except that 2-(4-bromophenyl)-furan (1h) was usedinstead of 2-[(1,1′-biphenyl)-4-ylmethyl]furan (1ac).

Colorless liquid; ¹H NMR (600 MHz, CDCl₃): δ 7.49 (d, J=6.4 Hz, 2H),7.43-7.38 (m, 3H), 7.35 (t, J=7.0 Hz, 2H), 7.11 (d, J=8.3 Hz, 2H), 2.71(dd, J=14.6, 6.4 Hz, 1H), 2.50 (dd, J=14.6, 7.0 Hz, 1H), 1.07-0.89 (m,1H), 0.68-0.54 (m, 2H), 0.21 (s, 3H), 0.17 (s, 3H), −0.15-−0.31 (m, 1H);¹³C NMR (150 MHz, CDCl₃): δ 141.0, 139.1, 133.8, 131.4, 130.3, 129.0,127.8, 119.8, 41.1, 16.9, 9.3, 3.8, −3.6, −3.8; ²⁹Si NMR (120 MHz,CDCl₃): δ −2.9; HRMS (EI): Calculated for C₁₈H₂₁BrSi [M]⁺: 344.0596,Found: 344.0592.

Inventive Example 20 Preparation ofanti-2-{[(1,1′-Biphenyl)-4-ylmethyl]cyclopropyl}dimethylphenylsilane(Anti-45)

Anti-2-{[(1,1′-Biphenyl)-4-ylmethyl]cyclopropyl}dimethylphenylsilane(anti-45) (yield of 85%, dr.>99/1) was obtained using the same method asInventive Example 10 except that 2-(1,1′-biphenyl-4-yl)furan (1i) wasadded instead of 2-methylfuran at −78° C. and was subjected to areaction at 40° C. for 10 hours.

Colorless liquid; ¹H NMR (600 MHz, CDCl₃): δ 7.65 (d, J=7.6 Hz, 2H),7.58-7.51 (m, 4H), 7.49 (t, J=7.8 Hz, 2H), 7.43-7.28 (m, 6H), 2.85-2.73(m, 1H), 2.70-2.58 (m, 1H), 1.07 (q, J=5.8 Hz, 1H), 0.71-0.58 (m, 2H),0.24 (s, 3H), 0.21 (s, 3H), −0.11-−0.29 (m, 1H).); ¹³C NMR (150 MHz,CDCl₃): δ 141.2, 141.1, 139.1, 138.8, 133.8, 128.8, 128.7, 127.7,127.04, 127.02, 41.2, 16.9, 9.2, 3.6, −3.6, −3.7; ²⁹Si NMR (120 MHz,CDCl₃): δ −2.8; HRMS (EI): Calculated for C₂₄H₂₆Si [M]⁺: 342.1804,Found: 342.1801.

Inventive Example 21 Preparation ofanti-2-{[(4-Methylthio)benzyl]cyclopropyl}dimethylphenylsilane (Anti-46)

Anti-2-{[(4-Methylthio)benzyl]cyclopropyl}dimethylphenylsilane (anti-46)(yield of 90%, dr.>99/1) was obtained via a reaction using the samemethod as Inventive Example 10 except that 2-[4-(methylthio)phenyl]furan(1 m) was used instead of 2-methylfuran.

Colorless liquid; ¹H NMR (600 MHz, CDCl₃): δ 7.53 (d, J=7.0 Hz, 2H),7.41-7.36 (m, 3H), 7.25 (d, J=8.0 Hz, 2H), 7.20 (d, J=8.1 Hz, 2H), 2.74(dd, J=14.5, 6.4 Hz, 1H), 2.58 (dd, J=14.5, 6.9 Hz, 1H), 2.53 (s, 3H),1.07-0.99 (m, 1H), 0.66-0.58 (m, 2H), 0.24 (s, 3H), 0.21 (s, 3H),−0.14-−0.24 (m, 1H); ¹³C NMR (150 MHz, CDCl₃): δ 139.3, 135.5, 133.9,129.1, 127.8, 127.3, 41.1, 17.0, 16.54, 9.2, 3.7, −3.6, −3.7; ²⁹Si NMR(120 MHz, CDCl₃): δ −2.9; HRMS (EI): Calculated for C₁₉H₂₄SSi [M]⁺:312.1368, Found: 312.1366.

Inventive Example 22 Preparation ofanti-[2-(3-Methylbenzyl)cyclopropyl]dimethylphenylsilane (Anti-47)

Anti-[2-(3-Methylbenzyl)cyclopropyl]dimethylphenylsilane (anti-47)(yield of 83%, dr.>99/1) was obtained using the same method as InventiveExample 15 except that 2-(m-tolyl)furan (1k) was added instead of2-[(1,1′-biphenyl)-4-ylmethyl]furan (1ac) at −78° C.

Colorless liquid; ¹H NMR (600 MHz, CDCl₃): δ 7.50 (d, J=7.8 Hz, 2H),7.39-7.30 (m, 3H), 7.18 (t, J=7.5 Hz, 1H), 7.06 (s, 1H), 7.05-7.01 (m,2H), 2.69-2.63 (m, 1H), 2.61-2.49 (m, 1H), 2.34 (s, 3H), 1.05-0.89 (m,1H), 0.61-0.52 (m, 2H), 0.18 (s, 3H), 0.16 (s, 3H), −0.16-−0.30 (m 1H);¹³C NMR (150 MHz, CDCl₃): δ 141.9, 139.2, 137.7, 133.7, 129.1, 128.8,128.1, 127.6, 126.6, 125.4, 41.5, 21.4, 16.8, 9.1, 3.5, −3.7, −3.8; ²⁹SiNMR (120 MHz, CDCl₃): δ −2.9; HRMS (EI): Calculated for C₁₉H₂₄Si [M]⁺:280.1647, Found: 280.1648.

Inventive Example 23 Preparation ofanti-[2-(3,5-Dibromobenzyl)cyclopropyl]dimethylphenylsilane (Anti-48)

Anti-[2-(3,5-Dibromobenzyl)cyclopropyl]dimethylphenylsilane (anti-48)(yield of 81%, dr.>99/1) was obtained using the same method as InventiveExample 10 except that 2-(3,5-dibromophenyl)furan (1o) was added insteadof 2-methylfuran at −78° C. and was subjected to a reaction at 40° C.for 22 hours.

Colorless liquid; ¹H NMR (600 MHz, CDCl₃): δ 7.58-7.47 (m, 3H),7.43-7.36 (m, 3H), 7.34 (s, 2H), 2.72-2.64 (m, 1H), 2.52-2.43 (m, 1H),1.00-0.87 (m, 1H), 0.64-0.54 (m, 2H), 0.22 (s, 3H), 0.21 (s, 3H),−0.18-−0.27 (m, 1H); ¹³C NMR (150 MHz, CDCl₃): δ 146.0, 138.6, 133.7,131.6, 130.1, 129.0, 127.7, 122.7, 40.9, 16.4, 9.3, 3.9, −3.6, −3.8;²⁹Si NMR (120 MHz, CDCl₃): δ −2.9.

Inventive Example 24 Preparation ofanti-[2-(2,4,6-Triisopropylbenzyl)cyclopropyl]dimethylphenylsilane(Anti-49)

Anti-[2-(2,4,6-Triisopropylbenzyl)cyclopropyl]dimethylphenylsilane(anti-49) (yield of 77%, dr.>99/1) was obtained via a reaction using thesame method as Inventive Example 15 except that2-(2,4,6-triisopropylphenyl)furan (1p) was used instead of2-[(1,1′-biphenyl)-4-ylmethyl]furan (1ac).

colorless liquid; ¹H NMR (600 MHz, CDCl₃): δ 7.57 (d, J=7.3 Hz, 2H),7.45-7.33 (m, 3H), 7.06 (s, 2H), 3.35-3.26 (m, 2H), 3.02 (dd, J=14.5,4.2 Hz, 1H), 2.99-2.91 (m, 1H), 2.77 (dd, J=14.5, 6.3 Hz, 1H), 1.35 (s,3H), 1.34 (s, 3H), 1.30 (s, 6H), 1.29 (s, 6H), 0.96-0.87 (m, 1H),0.67-0.60 (m, 1H), 0.57-0.51 (m, 1H), 0.27 (s, 3H), 0.23 (s, 3H),−0.17-−0.29 (m, 1H); ¹³C NMR (150 MHz, CDCl₃): δ 147.0, 146.4, 139.3,133.9, 131.9, 128.9, 127.8, 120.9, 34.3, 30.9, 29.5, 24.7, 24.4, 24.3,16.8, 9.4, 2.6, −3.7; ²⁹Si NMR (120 MHz, CDCl₃): δ −2.7; HRMS (EI):Calculated for C₂₇H₄₀Si [M]⁺: 392.2899, Found: 392.2898.

Inventive Example 25 Preparation ofanti-[2-(Phenanthren-9-ylmethyl)cyclopropyl]dimethylphenylsilane(anti-50)

Anti-[2-(Phenanthren-9-ylmethyl)cyclopropyl]dimethylphenylsilane(anti-50) (yield of 81%, dr.>99/1) was obtained via a reaction for 10hours using the same method as Inventive Example 10 except that2-(phenanthren-9-yl)furan (1q) was used instead of 2-methylfuran.

Colorless liquid; ¹H NMR (600 MHz, CDCl₃): δ 8.78 (d, J=7.9 Hz, 1H),8.71 (d, J=8.0 Hz, 1H), 8.16 (d, J=7.9 Hz, 1H), 7.82 (d, J=7.6 Hz, 1H),7.75-7.57 (m, 5H), 7.51 (d, J=7.0 Hz, 2H), 7.35 (t, J=7.1 Hz, 1H), 7.28(t, J=7.4 Hz, 2H), 3.32 (dd, J=15.3, 5.9 Hz, 1H), 3.08 (dd, J=15.3, 6.7Hz, 1H), 1.41-1.25 (m, 1H), 0.79-0.67 (m, 2H), 0.25 (s, 3H), 0.21 (s,3H), −0.08-−0.11 (m, 1H); ¹³C NMR (150 MHz, CDCl₃): δ 139.2, 136.0,133.9, 132.1, 131.6, 130.7, 129.8, 128.9, 128.3, 127.8, 126.7, 126.6,126.2, 126.1, 125.9, 124.5, 123.3, 122.5, 38.7, 15.5, 9.7, 4.2, −3.5,−3.7; ²⁹Si NMR (120 MHz, CDCl₃): δ −2.8; HRMS (EI): Calculated forC₂₆H₂₆Si [M]⁺: 366.1804, Found: 366.1803.

Inventive Example 26 Preparation ofanti-{[(5-Bromo-1,3-phenylene)bis(methylene)]bis(cyclopropane-2,1-diyl)bis(dimethylphenylsilane)}(Anti-51)

Anti-{[(5-Bromo-1,3-phenylene)bis(methylene)]bis(cyclopropane-2,1-diyl)bis(dimethylphenylsilane)}(anti-51) (yield of 75%, dr.>99/1) was obtained via a reaction at 23° C.for 12 hours using the same method as Inventive Example 10 by adding2,2′-(5-bromo-1,3-phenylene)difuran (1s) instead of 2-methylfuran at−78° C. using 10.0 mol % B(C₆F₅)₃ and dimethylphenylsilane (8.0 eq.).

Colorless liquid; ¹H NMR (600 MHz, CDCl₃): δ 7.48 (d, J=6.2 Hz, 4H),7.39-7.29 (m, 6H), 7.24 (s, 2H), 6.97 (s, 1H), 2.61 (dd, J=14.7, 6.5 Hz,2H), 2.48 (dd, J=14.7, 6.8 Hz, 2H), 0.92 (q, J=6.7 Hz, 2H), 0.59-0.51(m, 4H), 0.17 (s, 12H), −0.26 (q, J=7.8 Hz, 2H); ¹³C NMR (150 MHz,CDCl₃): δ 144.1, 138.9, 133.7, 128.86, 128.84, 127.6, 127.2, 122.1,41.1, 16.6, 16.6, 9.16, 9.15, 3.7, −3.6, −3.8; ²⁹Si NMR (120 MHz,CDCl₃): δ −2.9; HRMS (EI): Calculated for C₃₀H₃₇BrSi₂ [M]⁺: 532.1617,Found: 532.1616.

Inventive Example 27 Preparation ofanti-1,3,5-Tris{[2-(dimethylphenylsilyl)cyclopropyl]methyl}benzene(Anti-52)

Anti-1,3,5-Tris{[2-(dimethylphenylsilyl)cyclopropyl]methyl}benzene(anti-52) (yield of 86%, dr.>99/1) was obtained via a reaction at 23° C.for 8 hours using the same method as Inventive Example 10 by adding1,3,5-tri(furan-2-yl)benzene (1t) instead of 2-methylfuran at −78° C.using 20.0 mol % B(C₆F₅)₃ and dimethylphenylsilane (12.0 eq.).

Colorless liquid; ¹H NMR (400 MHz, CDCl₃): δ 7.69-7.61 (m, 6H),7.50-7.42 (m, 9H), 7.11 (s, 3H), 2.82-2.61 (m, 6H), 1.21-1.00 (m, 3H),0.82-0.56 (m, 6H), 0.32 (s, 9H), 0.31 (s, 9H), 0.00-−0.23 (m, 3H); ¹³CNMR (150 MHz, CDCl₃): δ 141.8, 139.3, 133.8, 128.9, 127.7, 126.2, 41.6,17.0 (t, J=4.5 Hz, 3C), 9.2 (t, J=3.0 Hz, 3C), 3.6, −3.4, −3.6; ²⁹Si NMR(120 MHz, CDCl₃): δ −2.8; HRMS (PSI): Calculated for C₄₂H₅₄NaSi₃[M+Na]⁺: 665.3431, Found: 665.3432.

Inventive Example 28 Preparation of((1S,2S)-2-(2-([1,1′-biphenyl]-4-yl)ethyl)cyclopropyl)dimethyl(phenyl)silane(Anti-40)

((1S,2S)-2-(2-([1,1′-biphenyl]-4-yl)ethyl)cyclopropyl)dimethyl(phenyl)silane(anti-40) (yield of 71%, dr.>99/1) was obtained via a reaction for 10hours using the same method as Inventive Example 10 except that2-([1,1′-biphenyl]-4-ylmethyl)furan (1ac) was used instead of2-methylfuran.

¹H NMR (600 MHz, CDCl₃): δ 7.71 (t, J=7.0 Hz, 4H), 7.63 (d, J=8.0 Hz,2H), 7.54 (t, J=7.6 Hz, 2H), 7.50-7.46 (m, 3H), 7.44 (t, J=6.9 Hz, 1H),7.35 (d, J=7.9 Hz, 2H), 2.92-2.81 (m, 2H), 1.93-1.84 (m, 1H), 1.73-1.62(m, 1H), 0.94-0.82 (m, 1H), 0.67-0.52 (m, 2H), 0.35 (s, 3H), 0.33 (s,3H), −0.19-−0.28 (m, 1H); ¹³C NMR (150 MHz, CDCl₃): δ 141.8, 141.3,139.4, 138.7, 133.9, 128.9, 128.9, 128.8, 127.8, 127.1, 38.0, 35.9,15.9, 9.3, 3.9, −3.5, −3.6; ²⁹Si NMR (120 MHz, CDCl₃): δ −2.9; HRMS(ESI): Calculated for C₂₅H₂₃NaSi [M+Na]⁺: 379.1858, Found: 379.1852.

III. Preparation of Anti-Cyclopropyl Silane Derivative fromα-silyloxy-(Z)-alkenyl Silane Compound Inventive Example 29 Preparationof anti-(2-Ethylcyclopropyl)dimethylphenylsilane (Anti-33)

B(C₆F₅)₃ (154 mg, 3.0 mol %) was dissolved in CH₂Cl₂ (0.2 mL), Z-2 (3.54g, 10 mmol) and dimethylphenylsilane (2.0 g, 15 mmol) were sequentiallyadded thereto at 0° C. and, then, the reaction mixture was stirred underargon gas at 23° C. for 12 hours. A conversion yield of 83% was verifiedvia ¹H NMR analysis. After the reaction mixture was completely stirred,the reaction mixture was subjected to vacuum evaporation and waspurified via silica gel flash column chromatography (eluant: hexane ormixture of hexane and ethyl acetate) to obtainanti-(2-Ethylcyclopropyl)dimethylphenylsilane (anti-33) as a colorlessliquid (1.57 g, yield of 77%, dr.>99/1).

Inventive Example 30 Preparation ofanti-(2-Ethylcyclopropyl)dimethylphenylsilane-d (Anti-35-d)

Anti-(2-Ethylcyclopropyl)dimethylphenylsilane-d (anti-35-d) (yield of66%, dr.>99/1) was obtained via a reaction for 14 hours using the samemethod as Inventive Example 29 except that CD₂Cl₂ was used instead ofCH₂Cl₂, PhMe₂SiD was used instead of dimethylphenylsilane, and B(C₆F₅)₃was used in 5.0 mol %.

Colorless liquid; ¹H NMR (600 MHz, CD₂Cl₂): δ 7.66-7.59 (m, 2H),7.43-7.35 (m, 3H), 1.45-1.40 (m, 0.6H), 1.30-1.21 (m, 0.4H), 1.02 (d,J=7.5 Hz, 3H), 0.75-0.67 (m, 1H), 0.51-0.42 (m, 2H), 0.26 (s, 3H), 0.24(s, 3H), −0.33-−0.46 (m, 1H); ¹³C NMR (150 MHz, CD₂Cl₂): δ 140.1, 134.3,129.2, 128.1, 29.0 (t=19.6 Hz), 18.1, 14.1, 9.2, 3.6, −3.4, −3.7; ²⁹SiNMR (120 MHz, CD₂Cl₂): δ −3.1; ²H NMR (60 MHz, CD₂Cl₂): δ 1.58-1.36 (s,0.4D), 1.36-1.12 (s, 0.6D); HRMS (ESI): Calculated for C₁₃H₂₀DSi [M+H]⁺:206.1475, Found: 206.1428.

Inventive Example 31 Preparation of2-{2-[(1,1′-Biphenyl)-4-yl]ethyl}cyclopropyl methanesulfonate (Anti-63)

Preparation of anti-2-{2-[(1,1′-Biphenyl)-4-yl]ethyl}cyclopropanol(Anti-62)

B(C₆F₅)₃ (52 mg, 5.0 mol %) was dissolved in CH₂Cl₂ (1.0 mL), Ph₂SiH₂(2.21 g, 12.0 mmol) was added thereto and, then, the resultant wasstirred. 2-[(1,1′-biphenyl)-4-ylmethyl]furan (1ac, 234 mg, 4.0 mmol) wasadded thereto at 0° C. and the reaction mixture was stirred at 23° C.for 10 hours. Et₃N (5 eq based on B(C₆F₅)₃) was added to complete thereaction and, then, was subjected to vacuum evaporation. The evaporatedremaining material was immediately used in Tamao oxidation. Theevaporated remaining material was dissolved in THF/MeOH (20/20 mL), KF(2.32 g, 40 mmol), KHCO₃ (4.04 g, 40 mmol), and 30% of hydrogen peroxideaqueous solution (130 mmol, 16 mL) were added and, then, the resultantwas stirred at 23° C. for 16 hours.

10% of NaHSO₃ aqueous solution (20 mL) was added to the reaction mixtureat 0° C. to extract a water layer with diethyl ether(20 mL×3). Theobtained organic layer was washed with a saturated Na₂CO₃ aqueoussolution (20 mL×2), was dried with anhydrous MgSO₄, was filtered, andwas subjected to vacuum evaporation and, then, the remaining materialwas purified (to hexane/ethyl acetate 1/1) via silica gel columnchromatography (hexane/ethyl acetate 1/1) to obtainanti-2-{2-[(1,1′-Biphenyl)-4-yl]ethyl}cyclopropanol (anti-62) (621 g,65% for two steps, dr.>99/1).

Colorless solid; m.p. 91-92° C.; ¹H NMR (600 MHz, CDCl₃): δ 7.67-7.59(m, 2H), 7.58-7.53 (m, 2H), 7.46 (t, J=7.7 Hz, 2H), 7.41-7.34 (m, 1H),7.29 (d, J=7.9 Hz, 2H), 3.21 (dt, J=6.2, 2.6 Hz, 1H), 2.88-2.67 (m, 2H),2.15 (s, 1H), 1.67-1.56 (m, 1H), 1.54-1.45 (m, 1H), 1.10-0.94 (m, 1H),0.83-0.63 (m, 1H), 0.38 (q, J=6.0 Hz, 1H); ¹³C NMR (150 MHz, CDCl₃): δ141.4, 141.2, 138.8, 128.9, 128.81, 127.11 (2C), 127.07, 52.9, 35.0,33.6, 20.7, 14.5; HRMS (ESI): Calculated for C₁₇H₁₇ONa [M+Na]⁺:260.1177, Found 260.1179.

Preparation of 2-{2-[(1,1′-Biphenyl)-4-yl]ethyl}cyclopropylmethanesulfonate (Anti-63)

Triethylamine (Et₃N) (152 mg, 1.5 mmol), 4-dimethylaminopyridine (DMAP)(0.6 mg, 1 mol %), anti-62 (119 mg, 0.5 mmol), mesyl chloride (69 mg,0.6 mmol), and CH₂Cl₂ (1.0 mL) were mixed at 0° C. and, then, werestirred at 23° C. for 6 hours. Water (3 mL) was added to complete areaction and the reaction mixture was subjected to extraction withCH₂Cl₂ (3 mL×3). An organic layer was dried with Na₂SO₄, was filtered,and was subjected to vacuum evaporation and, then, the remainingmaterial was purified via silica gel column chromatography (hexane/ethylacetate 7/3) to obtain 2-{2-[(1,1′-Biphenyl)-4-yl]ethyl}cyclopropylmethanesulfonate (anti-63) (137 mg, 87%, dr.>99/1).

Brown solid; m.p. 63-65° C.; ¹H NMR (600 MHz, CDCl₃): δ 7.59 (d, J=7.8Hz, 2H), 7.53 (d, J=8.2 Hz, 2H), 7.44 (t, J=7.7 Hz, 2H), 7.36-7.31 (m,1H), 7.27 (d, J=7.8 Hz, 2H), 4.08-3.72 (m, 1H), 2.98 (s, 3H), 2.79 (t,J=7.6 Hz, 2H), 1.71-1.53 (m, 2H), 1.42-1.31 (m, 1H), 1.16-1.06 (m, 1H),0.66 (q, J=6.7 Hz, 1H); ¹³C NMR (150 MHz, CDCl₃): δ 140.9, 140.4, 138.9,128.8, 128.7, 127.1, 127.1, 126.9, 58.7, 37.6, 34.3, 32.7, 18.1, 12.1;HRMS (ESI): Calculated for C₁₈H₂₀NaO₃S [M+Na]⁺: 339.1031, Found:339.1024.

1. A method of preparing a silane derivative represented by ChemicalFormula 1, the method comprising preparing Chemical Formula 1 via areaction between Chemical Formula 2 and Chemical Formula 3 in thepresence of a borane catalyst:

wherein, in Chemical Formulae 1 to 3, R₁ is C₁-C₁₀ alkyl or C₆-C₂₀ arylwith a radical number depending on n; R₁₁ to R₁₃ are each independentlyC₁-C₁₀ alkyl or C₆-C₁₂ aryl; n is an integer of 1 to 3 and, when n isequal to or greater than 2, R₁ is aryl; and alkyl and aryl of R₁ arefurther substituted with any one selected from halogen, C₁-C₁₀ alkyl,halo C₁-C₁₀ alkyl, thio C₁-C₁₀ alkyl, C₁-C₁₀ alkoxy, C₆-C₁₂ aryl, C₆-C₁₂aryloxy, and —OSi(R₂₁)(R₂₂)(R₂₃) and R₂₁ to R₂₃ are each independentlyC₁-C₁₀ alkyl or C₆-C₁₂ aryl.
 2. The method of claim 1, wherein ChemicalFormula 1 is represented by Chemical Formula 1-1 and Chemical Formula 2is represented by Chemical Formula 2-1:

wherein, in Chemical Formulae 1-1 and 2-1, R₂ is C₁-C₁₀ alkyl or C₆-C₁₈aryl; R₁₁ to R₁₃ are each independently C₁-C₁₀ alkyl or C₆-C₁₂ aryl; andalkyl and aryl of R₂ are further substituted with any one selected fromhalogen, C₁-C₁₀ alkyl, halo C₁-C₁₀ alkyl, thio C₁-C₁₀ alkyl, C₁-C₁₀alkoxy, C₆-C₁₂ aryl, C₆-C₁₂ aryloxy, and —OSi(R₂₁)(R₂₂)(R₂₃) and R₂₁ toR₂₃ are each independently C₁-C₁₀ alkyl or C₆-C₁₂ aryl.
 3. The method ofclaim 1, wherein Chemical Formula 1 is represented by Chemical Formula1-2 and Chemical Formula 2 is represented by Chemical Formula 2-2:

wherein, in Chemical Formulae 1-2 and 2-2, R₁₁ to R₁₃ are eachindependently C₁-C₁₀ alkyl or C₆-C₁₂ aryl; n is an integer of 1 to 3;R₁₄ is halogen, C₁-C₁₀ alkyl, halo C₁-C₁₀ alkyl, thio C₁-C₁₀ alkyl,C₁-C₁₀ alkoxy, C₆-C₁₂ aryl, C₆-C₁₂ aryloxy, or —OSi(R₂₁)(R₂₂)(R₂₃); R₂₁to R₂₃ are each independently C₁-C₁₀ alkyl or C₆-C₁₂ aryl; and s is aninteger of 0 or 1 to 4 and n+s≤6.
 4. (canceled)
 5. (canceled) 6.(canceled)
 7. (canceled)
 8. (canceled)
 9. The method of claim 1, whereinthe borane catalyst is B(C₆F₅)₃, (C₆F₅CH₂CH₂)B(C₆F₅)₂,(CF₃(CF₂)₃(CH₂)₂B(C₆F₅)₂, HB(C₆F₅)₂, B(C₆H₅)₃, or ClB(C₆F₅)₂.
 10. Themethod of claim 1, wherein the borane catalyst is used in 0.01 to 0.03mol based on 1 mol of the compound of Chemical Formula 2, ChemicalFormula 5, Chemical Formula 7, Chemical Formula 9, or Chemical Formula11.
 11. The method of claim 1, wherein: Chemical Formula 3 is used in2.0 to 2.5 moles based on 1 mol of the compound of Chemical Formula 2,Chemical Formula 5, Chemical Formula 7, or Chemical Formula 11; andChemical Formula 3-1 is used in 2.0 to 2.5 moles based on 1 mol of thecompound of Chemical Formula
 9. 12. The method of claim 1, wherein theborane catalyst is B(C₆F₅)₃ and Chemical Formula 3 is PhMe₂SiH. 13.(canceled)
 14. (canceled)
 15. A method of preparing ananti-(2-alkyl)cyclopropyl silane derivative of Chemical Formula 21-1 viaa reaction between a furan compound represented by Chemical Formula 22-1and a silane compound represented by Chemical Formula 23 in the presenceof a borane catalyst:

wherein, in Chemical Formulae 21-1, 22-1, and 23, R is C₁-C₂₀ alkyl,C₆-C₂₀ aryl, or C₆-C₂₀ aryl C₁-C₂₀ alkyl, and alkyl, aryl, or arylalkylof R is further substituted with one or more selected from the groupconsisting of halogen, C₁-C₂₀ alkyl, halo C₁-C₂₀ alkyl, C₁-C₂₀ alkoxy,C₆-C₂₀ aryl, C₆-C₂₀ aryloxy, and C₁-C₂₀ alkylthio; R^(a) to R^(c) areeach independently hydrogen, C₁-C₂₀ alkyl, or C₆-C₂₀ aryl; R^(d) ishydrogen or heavy hydrogen; and R^(a) to R^(c) are not simultaneouslyhydrogen.
 16. A method of preparing an anti-(2-alkyl)cyclopropyl silanederivative of Chemical Formula 21-1 via a reaction between anα-silyloxy-(Z)-alkenyl silane derivative represented by Chemical Formula24 and a silane compound represented by Chemical Formula 23 in thepresence of a borane catalyst:

wherein, in Chemical Formulae 21-1, 23, and 24, R is C₁-C₂₀ alkyl,C₆-C₂₀ aryl, or C₆-C₂₀ aryl C₁-C₂₀ alkyl, and alkyl, aryl, or arylalkylof R is further substituted with one or more selected from the groupconsisting of halogen, C₁-C₂₀ alkyl, halo C₁-C₂₀ alkyl, C₁-C₂₀ alkoxy,C₆-C₂₀ aryl, C₆-C₂₀ aryloxy, and C₁-C₂₀ alkylthio; R₁₁ to R₁₃ are eachindependently C₁-C₂₀ alkyl or C₆-C₂₀ aryl; R^(a) to R^(c) are eachindependently hydrogen, C₁-C₂₀ alkyl, or C₆-C₂₀ aryl; R^(d) is hydrogenor heavy hydrogen; and R^(a) to R^(c) are not simultaneously hydrogen.17. (canceled)
 18. (canceled)
 19. The method of claim 15, wherein theborane catalyst is B(C₆F₅)₃ or B(C₆F₅)₂R³¹, R³¹ is hydrogen, halogen,C₁-C₁₀ alkyl, or C₁-C₁₂ aryl, and alkyl or aryl of R¹¹ is furthersubstituted with halo C₁-C₁₀ alkyl halo C₆-C₁₂.
 20. The method of claim15, wherein the borane catalyst is used in 3.0 to 7.0 mol % based on 1mol of the furan compound of Chemical Formula 22-1.
 21. The method ofclaim 16, wherein the borane catalyst is used in 3.0 to 7.0 mol % basedon 1 mol of the α-silyloxy-(Z)-alkenyl silane derivative of ChemicalFormula
 24. 22. (canceled)
 23. (canceled)
 24. The method of claim 15,wherein the silane compound of Chemical Formula 23 is used in 1 to 5moles based on 1 mol of the furan compound of Chemical Formula 22-1. 25.The method of claim 16, wherein the silane compound of Chemical Formula23 is used in 1 to 5 moles based on 1 mol of the α-silyloxy-(Z)-alkenylsilane derivative of Chemical Formula
 24. 26. (canceled)
 27. (canceled)28. The method of claim 15, wherein a reaction temperature is −78° C. to50° C.
 29. (canceled)
 31. The method of claim 16, wherein the boranecatalyst is B(C₆F₅)₃ or B(C₆F₅)₂R³¹, R³¹ is hydrogen, halogen, C₁-C₁₀alkyl, or C₁-C₁₂ aryl, and alkyl or aryl of R¹¹ is further substitutedwith halo C₁-C₁₀ alkyl halo C₆-C₁₂.
 32. The method of claim 16, whereina reaction temperature is −78° C. to 50° C.